CN105032464B - Carbonitride metatitanic acid nickel composite material and preparation method and application - Google Patents
Carbonitride metatitanic acid nickel composite material and preparation method and application Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 4
- 239000002253 acid Substances 0.000 title description 2
- 229910052759 nickel Inorganic materials 0.000 title description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 85
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000002351 wastewater Substances 0.000 claims abstract description 31
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 claims abstract description 22
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 21
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 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 11
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000006731 degradation reaction Methods 0.000 claims description 17
- 230000015556 catabolic process Effects 0.000 claims description 14
- 229910052724 xenon Inorganic materials 0.000 claims description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical group [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000013032 photocatalytic reaction Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
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- 150000001875 compounds Chemical class 0.000 claims description 3
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- 230000001699 photocatalysis Effects 0.000 abstract description 21
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- 229920000642 polymer Polymers 0.000 description 6
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- 238000001179 sorption measurement Methods 0.000 description 5
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- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
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- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
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- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical group O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种氮化碳‑钛酸镍复合材料及其制备方法与应用，该氮化碳‑钛酸镍复合材料包括氮化碳和钛酸镍，钛酸镍沉积于氮化碳表面构成氮化碳‑钛酸镍复合材料。制备方法包括以下步骤：将双氰胺溶于乙二醇中，得到含双氰胺的乙二醇溶液；将醋酸镍和钛酸四丁酯加入双氰胺的乙二醇溶液进行聚合反应得到反应产物；将反应产物煅烧得到氮化碳‑钛酸镍复合材料。本发明的复合材料具有稳定性强、循环利用性高，具有高的比表面积以及高的光催化活性位点等优点，其制备方法工艺简单、操作性高、成本低，制备的复合材料具有优越的光催化性能，广泛应用于光催化降解染料废水领域。
The invention discloses a carbon nitride-nickel titanate composite material and its preparation method and application. The carbon nitride-nickel titanate composite material includes carbon nitride and nickel titanate, and nickel titanate is deposited on the surface of carbon nitride Constitute carbon nitride-nickel titanate composite material. The preparation method comprises the following steps: dissolving dicyandiamide in ethylene glycol to obtain an ethylene glycol solution containing dicyandiamide; adding nickel acetate and tetrabutyl titanate to the ethylene glycol solution of dicyandiamide for polymerization reaction to obtain A reaction product; calcining the reaction product to obtain a carbon nitride-nickel titanate composite material. The composite material of the present invention has the advantages of strong stability, high recyclability, high specific surface area and high photocatalytic active sites, etc., and its preparation method is simple in process, high in operability and low in cost, and the prepared composite material has superior Its photocatalytic performance is widely used in the field of photocatalytic degradation of dye wastewater.
Description
技术领域technical field
本发明属于复合材料的制备技术领域，涉及一种光催化纳米复合材料及其制备方法与应用，具体涉及到一种氮化碳-钛酸镍复合材料及其制备方法与应用。The invention belongs to the technical field of preparation of composite materials, and relates to a photocatalytic nano composite material and its preparation method and application, in particular to a carbon nitride-nickel titanate composite material and its preparation method and application.
背景技术Background technique
近年来，光催化技术已广泛应用于处理废水中的无机和有机污染物。很多光催化材料如金属氧化物，硫化物和氮化物已得到了广泛的关注和研究。在这些光催化剂中，钙钛矿氧化物具有稳定的结构，在光催化领域表现出良好的光催化活性。其中，钛酸镍（NiTiO3）属于钛铁矿结构的三角晶系，以其适合的带隙（2.18 eV）和很好的太阳光响应特性，在光催化领域有潜在的应用前景。然而单独将钛酸镍作为光催化剂时，由于其较窄的带隙能量和较低的量子效率而导致其光催化活性不高。因此，通过与其它材料复合去改善NiTiO3的光催化性能变得非常必要。In recent years, photocatalytic technology has been widely used to treat inorganic and organic pollutants in wastewater. Many photocatalytic materials such as metal oxides, sulfides and nitrides have received extensive attention and research. Among these photocatalysts, perovskite oxides have a stable structure and exhibit good photocatalytic activity in the field of photocatalysis. Among them, nickel titanate (NiTiO 3 ) belongs to the triangular crystal system of ilmenite structure. With its suitable band gap (2.18 eV) and good sunlight response characteristics, it has potential application prospects in the field of photocatalysis. However, when nickel titanate is used alone as a photocatalyst, its photocatalytic activity is not high due to its narrow band gap energy and low quantum efficiency. Therefore, it is necessary to improve the photocatalytic performance of NiTiO 3 by combining with other materials.
石墨相氮化碳（g-C3N4）是一种新型无金属聚合物，具有层叠的二维结构，较小的带隙（2.7 eV）以及光响应范围广的半导体光催化剂。因此，g-C3N4可用来作为一种有效的助催化剂提高半导体材料的光催化活性。Graphite-phase carbon nitride (gC 3 N 4 ) is a novel metal-free polymer with a stacked two-dimensional structure, a small band gap (2.7 eV), and a semiconductor photocatalyst with a wide range of photoresponse. Therefore, gC 3 N 4 can be used as an effective co-catalyst to enhance the photocatalytic activity of semiconductor materials.
迄今为止，g-C3N4/NiTiO3复合材料的合成工作尚未见报道。鉴于此，开发和提供一种制备工艺简单、性能优良的g-C3N4/NiTiO3复合材料是非常必要的。So far, the synthesis of gC 3 N 4 /NiTiO 3 composites has not been reported. In view of this, it is very necessary to develop and provide a gC 3 N 4 /NiTiO 3 composite material with simple preparation process and excellent performance.
发明内容Contents of the invention
本发明要解决的技术问题是克服现有技术的不足，提供一种光催化性能优异、稳定性强、循环利用性高，具有高的比表面积以及高的光催化活性位点的氮化碳-钛酸镍复合材料，还提供了一种制备工艺简单、操作性高、成本低的氮化碳-钛酸镍复合材料的制备方法以及该氮化碳-钛酸镍复合材料在降解染料废水中的应用。The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a carbon nitride- The nickel titanate composite material also provides a method for preparing a carbon nitride-nickel titanate composite material with simple preparation process, high operability and low cost, and the carbon nitride-nickel titanate composite material can be used in the degradation of dye wastewater Applications.
为解决上述技术问题，本发明采用以下技术方案：In order to solve the problems of the technologies described above, the present invention adopts the following technical solutions:
一种氮化碳-钛酸镍复合材料，所述氮化碳-钛酸镍复合材料包括氮化碳和钛酸镍，所述钛酸镍沉积于所述氮化碳表面构成氮化碳-钛酸镍复合材料。A carbon nitride-nickel titanate composite material, the carbon nitride-nickel titanate composite material includes carbon nitride and nickel titanate, and the nickel titanate is deposited on the carbon nitride surface to form carbon nitride-nickel titanate Nickel titanate composite.
上述的氮化碳-钛酸镍复合材料，优选的，所述氮化碳的质量分数为10%～27.3%。In the above-mentioned carbon nitride-nickel titanate composite material, preferably, the mass fraction of the carbon nitride is 10%-27.3%.
作为本发明的同一技术构思，本发明还提供了一种氮化碳-钛酸镍复合材料的制备方法，包括以下步骤：As the same technical idea of the present invention, the present invention also provides a preparation method of carbon nitride-nickel titanate composite material, comprising the following steps:
（1）将双氰胺溶于乙二醇中，得到含双氰胺的乙二醇溶液；(1) Dicyandiamide is dissolved in ethylene glycol to obtain an ethylene glycol solution containing dicyandiamide;
（2）将醋酸镍和钛酸四丁酯加入步骤（1）所得的含双氰胺的乙二醇溶液进行聚合反应得到反应产物；(2) adding nickel acetate and tetrabutyl titanate to the dicyandiamide-containing ethylene glycol solution obtained in step (1) for polymerization reaction to obtain a reaction product;
（3）将所述步骤（2）所得的反应产物煅烧得到氮化碳-钛酸镍复合材料。(3) Calcining the reaction product obtained in the step (2) to obtain a carbon nitride-nickel titanate composite material.
乙二醇（EG）是一个双齿配体，能与金属离子形成链状结构的金属乙醇酸的聚合物。在上述步骤（2）的聚合反应过程中，钛酸镍，钛酸四丁酯，乙二醇生成Ni-Ti-EG聚合物。Ethylene glycol (EG) is a bidentate ligand that can form a chain-like metal glycolic acid polymer with metal ions. During the polymerization reaction in the above step (2), nickel titanate, tetrabutyl titanate, and ethylene glycol generate Ni-Ti-EG polymer.
上述的制备方法，优选的，所述步骤（1）中所述含双氰胺的乙二醇溶液中双氰胺的浓度为1.5g/L～5g/L。In the above preparation method, preferably, the concentration of dicyandiamide in the dicyandiamide-containing ethylene glycol solution in the step (1) is 1.5 g/L-5 g/L.
上述的制备方法，优选的，所述步骤（2）中，所述醋酸镍和钛酸四丁酯的摩尔比为1∶1。醋酸镍和钛酸四丁酯的摩尔比高于1∶1则醋酸镍过量，会生出杂质氧化镍；醋酸镍和钛酸四丁酯的摩尔比低于1∶1则钛酸四丁酯过量，会产生二氧化钛。In the above preparation method, preferably, in the step (2), the molar ratio of nickel acetate to tetrabutyl titanate is 1:1. If the molar ratio of nickel acetate and tetrabutyl titanate is higher than 1:1, the excess of nickel acetate will produce impurity nickel oxide; if the molar ratio of nickel acetate to tetrabutyl titanate is lower than 1:1, the excess of tetrabutyl titanate will occur. , producing titanium dioxide.
上述的制备方法，优选的，所述步骤（2）还包括反应产物的后处理步骤，具体为：将所述反应产物用乙醇洗涤后，在温度为40℃～60℃的环境下干燥6h～12h。In the above-mentioned preparation method, preferably, the step (2) further includes a post-treatment step of the reaction product, specifically: after washing the reaction product with ethanol, it is dried at a temperature of 40°C to 60°C for 6 hours to 12h.
上述的制备方法，优选的，所述步骤（2）中，所述煅烧过程中，以5℃/min～10℃/min的升温速率升温至550℃～560℃。In the above preparation method, preferably, in the step (2), during the calcination process, the temperature is raised to 550°C-560°C at a heating rate of 5°C/min-10°C/min.
上述的制备方法，优选的，所述步骤（2）中，煅烧时间为2h～3h，煅烧温度为550℃～560℃。煅烧温度高于600℃氮化碳容易发生热损失，煅烧温度低于550℃会影响钛酸镍的生成，因此，优选的煅烧温度为550℃～560℃。In the above preparation method, preferably, in the step (2), the calcination time is 2h-3h, and the calcination temperature is 550°C-560°C. If the calcination temperature is higher than 600°C, carbon nitride is prone to heat loss, and if the calcination temperature is lower than 550°C, the formation of nickel titanate will be affected. Therefore, the preferred calcination temperature is 550°C-560°C.
作为本发明的同一技术构思，本发明还提供了一种上述的氮化碳-钛酸镍复合材料或上述的制备方法制备得到的氮化碳-钛酸镍复合材料在降解废水中的硝基苯的应用。As the same technical idea of the present invention, the present invention also provides a kind of carbon nitride-nickel titanate composite material mentioned above or the carbon nitride-nickel titanate composite material prepared by the above preparation method. Benzene application.
上述的应用，优选的，包括以下步骤：将所述氮化碳-钛酸镍复合材料和乙醇添加到废水中，在可见光下进行光催化反应，完成对有机污染物的降解，所述氮化碳-钛酸镍复合材料的添加量为0.3g/L～0.6g/L，所述乙醇的添加量为2v/v%～5v/v%。The above-mentioned application preferably includes the following steps: adding the carbon nitride-nickel titanate composite material and ethanol to the wastewater, performing a photocatalytic reaction under visible light to complete the degradation of organic pollutants, the nitriding The added amount of the carbon-nickel titanate composite material is 0.3g/L-0.6g/L, and the added amount of the ethanol is 2v/v%-5v/v%.
上述的应用，优选的，在避光条件下将所述氮化碳-钛酸镍复合材料添加到废水中并搅拌。For the above application, preferably, the carbon nitride-nickel titanate composite material is added to the wastewater and stirred under the condition of avoiding light.
上述的应用，优选的，所述可见光的光源为300W～500W的氙灯。For the above application, preferably, the visible light source is a 300W-500W xenon lamp.
上述的应用，优选的，所述氙灯与所述废水的液面距离为14cm～16cm。For the above application, preferably, the liquid surface distance between the xenon lamp and the waste water is 14cm-16cm.
上述的应用，优选的，所述光催化反应的时间为60min～120min。For the above application, preferably, the time for the photocatalytic reaction is 60 minutes to 120 minutes.
上述的应用，优选的，所述废水中硝基苯的浓度为20mg/L～40mg/L。For the above application, preferably, the concentration of nitrobenzene in the wastewater is 20 mg/L-40 mg/L.
与现有技术相比，本发明的优点在于：Compared with the prior art, the present invention has the advantages of:
1、本发明提供了一种氮化碳-钛酸镍复合材料，稳定性强、循环利用性高，具有高的比表面积以及高的光催化活性，高比表面积可以为吸附污染物提供更多的活性位点，有助于光催化，因此，本发明的氮化碳-钛酸镍复合材料在光催化降解废水中污染物具有潜在应用；且以一维结构的NiTiO3纳米棒作为基体，相比于零维、二维和三维结构，其具有传输电子速率快、光吸收强、强度大、不易团聚以及吸附面积大等优点。1. The present invention provides a carbon nitride-nickel titanate composite material, which has strong stability, high recyclability, high specific surface area and high photocatalytic activity, and the high specific surface area can provide more pollutants for adsorption. active sites, contribute to photocatalysis, therefore, the carbon nitride -nickel titanate composite material of the present invention has potential applications in photocatalytic degradation of pollutants in wastewater; Compared with zero-dimensional, two-dimensional and three-dimensional structures, it has the advantages of fast electron transfer rate, strong light absorption, high strength, difficult to agglomerate, and large adsorption area.
2、本发明提供了一种氮化碳-钛酸镍复合材料的制备方法，利用乙二醇媒介路线结合煅烧的方法制备氮化碳-钛酸镍复合材料，乙二醇是一个双齿配体，能与金属离子形成链状结构的金属乙醇酸的聚合物；本发明在在乙二醇的作用下，钛酸镍，钛酸四丁酯，乙二醇生成Ni-Ti-EG聚合物，Ni-Ti-EG聚合物经过煅烧后得到氮化碳-钛酸镍复合材料。本发明的制备方法工艺简单，其反应条件容易控制、操作方法简单及成本低廉。2. The present invention provides a method for preparing a carbon nitride-nickel titanate composite material. The carbon nitride-nickel titanate composite material is prepared by using the ethylene glycol medium route combined with calcination. Ethylene glycol is a bidentate compound. Body, the polymer of metal glycolic acid that can form a chain structure with metal ions; the present invention generates Ni-Ti-EG polymer under the action of ethylene glycol, nickel titanate, tetrabutyl titanate, and ethylene glycol , Ni-Ti-EG polymer was calcined to obtain carbon nitride-nickel titanate composite material. The preparation method of the invention has simple process, easy control of reaction conditions, simple operation method and low cost.
3、本发明的氮化碳-钛酸镍复合材料在可见光下具有很好的光催化性能，可广泛用于光降解染料废水领域，特别适用于光降解硝基苯染料废水，具有工艺简单、操作便捷、催化效果好等优点。3. The carbon nitride-nickel titanate composite material of the present invention has good photocatalytic performance under visible light, and can be widely used in the field of photodegradation dye wastewater, especially suitable for photodegradation of nitrobenzene dye wastewater, with simple process, It has the advantages of convenient operation and good catalytic effect.
附图说明Description of drawings
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整的描述。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention.
图1为g-C3N4、NiTiO3以及本发明实施例1中的氮化碳-钛酸镍复合材料对应的XRD衍射图谱。Fig. 1 is the XRD diffraction patterns corresponding to gC 3 N 4 , NiTiO 3 and the carbon nitride-nickel titanate composite material in Example 1 of the present invention.
图2为g-C3N4、NiTiO3以及本发明实施例1中的氮化碳-钛酸镍复合材料对应的SEM图。Fig. 2 is a SEM image corresponding to gC 3 N 4 , NiTiO 3 and the carbon nitride-nickel titanate composite material in Example 1 of the present invention.
图3为g-C3N4、NiTiO3以及本发明实施例1～3中的氮化碳-钛酸镍复合材料对应的紫外-可见漫反射吸收光谱图。Fig. 3 is an ultraviolet-visible diffuse reflection absorption spectrum corresponding to gC 3 N 4 , NiTiO 3 and the carbon nitride-nickel titanate composite material in Examples 1-3 of the present invention.
图4为本发明中的氮化碳-钛酸镍复合材料光催化降解废水中的硝基苯的降解原理图。Fig. 4 is a schematic diagram of the photocatalytic degradation of nitrobenzene in waste water by the carbon nitride-nickel titanate composite material in the present invention.
图5为g-C3N4、NiTiO3以及本发明实施例1中的氮化碳-钛酸镍复合材料光催化降解废水中的硝基苯对应的时间-降解效率的关系图。Fig. 5 is a time-degradation efficiency relation diagram corresponding to the photocatalytic degradation of nitrobenzene in waste water by gC 3 N 4 , NiTiO 3 and the carbon nitride-nickel titanate composite material in Example 1 of the present invention.
图6为本发明实施例1～3中的氮化碳-钛酸镍复合材料光催化降解废水中的硝基苯对应的时间-降解效率的关系图。Fig. 6 is a time-degradation efficiency relation graph corresponding to the photocatalytic degradation of nitrobenzene in waste water by the carbon nitride-nickel titanate composite material in Examples 1-3 of the present invention.
图7是本发明实施例1中的氮化碳-钛酸镍复合材料循环反应五次的光催化性能曲线。Fig. 7 is the photocatalytic performance curve of the carbon nitride-nickel titanate composite material in Example 1 of the present invention after five cycles of reaction.
具体实施方式detailed description
以下结合说明书附图和具体优选的实施例对本发明作进一步描述，但并不因此而限制本发明的保护范围。The present invention will be further described below in conjunction with the accompanying drawings and specific preferred embodiments, but the protection scope of the present invention is not limited thereby.
实施例Example
以下实施例中所采用的材料和仪器均为市售。All materials and instruments used in the following examples are commercially available.
实施例1：Example 1:
一种本发明的氮化碳-钛酸镍复合材料，包括氮化碳和钛酸镍，其中氮化碳为块状，钛酸镍为棒状，棒状的钛酸镍沉积于块状的氮化碳表面，其中氮化碳的质量分数为18.4%。A carbon nitride-nickel titanate composite material of the present invention comprises carbon nitride and nickel titanate, wherein the carbon nitride is block-shaped, nickel titanate is rod-shaped, and the rod-shaped nickel titanate is deposited on the block-shaped nitrided Carbon surface, in which the mass fraction of carbon nitride is 18.4%.
分别对g-C3N4、NiTiO3以及本实施例的氮化碳-钛酸镍复合材料（g-C3N4/NiTiO3）的比表面积进行检测，通过BET的测量，g-C3N4、NiTiO3以及本实施例的氮化碳-钛酸镍复合材料（g-C3N4/NiTiO3）的比表面积分别为10.238 m2 g−1，57.138 m2 g−1，61.284 m2 g−1，可见g-C3N4/NiTiO3材料的比表面积比两个单体大；高比表面积可以为吸附污染物提供更多的活性位点，这有助于光催化，因此，本发明的氮化碳-钛酸镍复合材料具有高的光催化活性。The specific surface areas of gC 3 N 4 , NiTiO 3 and the carbon nitride-nickel titanate composite material (gC 3 N 4 /NiTiO 3 ) of this example were detected respectively. Through BET measurement, gC 3 N 4 , NiTiO 3 And the specific surface areas of the carbon nitride-nickel titanate composite material (gC 3 N 4 /NiTiO 3 ) in this example are 10.238 m 2 g −1 , 57.138 m 2 g −1 , and 61.284 m 2 g −1 , respectively. It can be seen that The specific surface area of the gC 3 N 4 /NiTiO 3 material is larger than that of the two monomers; the high specific surface area can provide more active sites for adsorbing pollutants, which is helpful for photocatalysis. Therefore, the carbon nitride of the present invention- Nickel titanate composites have high photocatalytic activity.
一种上述本实施例的氮化碳-钛酸镍复合材料的制备方法，包括以下步骤：A preparation method of the carbon nitride-nickel titanate composite material of the above-mentioned present embodiment, comprising the following steps:
（1）称取300mg双氰胺搅拌溶于100ml乙二醇溶液中，得到含双氰胺的乙二醇溶液；(1) Weigh 300mg of dicyandiamide, stir and dissolve it in 100ml of ethylene glycol solution to obtain an ethylene glycol solution containing dicyandiamide;
（2）将2.48g醋酸镍和3.4mL钛酸四丁酯加入步骤（1）所得的含双氰胺的乙二醇溶液中，不断搅拌，待溶液由绿变蓝后，再持续搅拌2h以确保反应完全，然后离心，倒掉上清液，得反应产物；(2) Add 2.48g of nickel acetate and 3.4mL of tetrabutyl titanate into the dicyandiamide-containing ethylene glycol solution obtained in step (1), and keep stirring until the solution changes from green to blue, then continue to stir for at least 2 hours. Make sure the reaction is complete, then centrifuge, pour off the supernatant, and get the reaction product;
（3）采用乙醇对步骤（2）所得反应产物进行洗涤离心，得蓝色前躯体凝聚物，将蓝色前躯体凝聚物置于干燥箱中以60℃真空干燥6h得前躯体；(3) Wash and centrifuge the reaction product obtained in step (2) with ethanol to obtain a blue precursor condensate, which is placed in a drying oven and vacuum-dried at 60°C for 6 hours to obtain a precursor;
（4）将步骤（3）所得的前躯体放入马弗炉内，以5℃/min的升温速率升温至550℃开始煅烧，煅烧时间为2h，煅烧完后自然冷却，将产物取出，用研钵研磨至粉末状，得到氮化碳-钛酸镍复合材料。(4) Put the precursor obtained in step (3) into a muffle furnace, heat up to 550°C at a heating rate of 5°C/min and start calcining for 2 hours. Cool naturally after calcining, take out the product, and use Grinding in a mortar to powder to obtain a carbon nitride-nickel titanate composite material.
图1为g-C3N4、NiTiO3以及本实施例的氮化碳-钛酸镍复合材料（g-C3N4/NiTiO3-18.4%）对应的XRD衍射图谱。从图中可以看出，单纯g-C3N4在27.4°处存在明显的衍射峰，它对应于g-C3N4的特征衍射峰（100）。对图中NiTiO3谱线进行分析得出，在衍射角约为24.1°，33.1°，35.7°，40.9°，49.5°，54.0°， 62.5°和64.0°处，存在（012），（104），（110），（113），（024），（116），（214）和（300）的峰， NiTiO3的衍射峰对应于卡片（JCPDS no. 33-0960）。而g-C3N4/NiTiO3的XRD衍射图谱呈现了g-C3N4和NiTiO3的所有特征衍射峰。Fig. 1 is the XRD diffraction patterns corresponding to gC 3 N 4 , NiTiO 3 and the carbon nitride-nickel titanate composite material (gC 3 N 4 /NiTiO 3 -18.4%) of this embodiment. It can be seen from the figure that pure gC 3 N 4 has an obvious diffraction peak at 27.4°, which corresponds to the characteristic diffraction peak (100) of gC 3 N 4 . According to the analysis of the NiTiO 3 spectral lines in the figure, there are (012), (104) , (110), (113), (024), (116), (214) and (300) peaks, and the diffraction peaks of NiTiO 3 correspond to the card (JCPDS no. 33-0960). The XRD diffraction pattern of gC 3 N 4 /NiTiO 3 presents all the characteristic diffraction peaks of gC 3 N 4 and NiTiO 3 .
图2为g-C3N4、NiTiO3以及本实施例的氮化碳-钛酸镍复合材料（-C3N4/NiTiO3-18.4%）对应的SEM图。其中（a）图为g-C3N4，（b）图为NiTiO3，（c）图和（d）图为本实施例的氮化碳-钛酸镍复合材料。从（a）图中可以看出，g-C3N4呈不规则块状，从（b）图中可以看出，NiTiO3呈大小不一的棒状，从（c）图和（d）图可以看出部分棒状NiTiO3沉积在块状g-C3N4表面，部分则出现在块状g-C3N4的块与块之间的间隙中。Fig. 2 is a SEM image corresponding to gC 3 N 4 , NiTiO 3 and the carbon nitride-nickel titanate composite material (-C 3 N 4 /NiTiO 3 -18.4%) of this embodiment. Among them, (a) picture shows gC 3 N 4 , (b) picture shows NiTiO 3 , (c) picture and (d) picture show the carbon nitride-nickel titanate composite material of this embodiment. It can be seen from the figure (a) that gC 3 N 4 is in the form of irregular blocks. It can be seen from the figure (b) that NiTiO 3 is in the shape of rods of different sizes. It can be seen from the figures (c) and (d) It can be seen that part of the rod-like NiTiO 3 is deposited on the surface of the block-like gC 3 N 4 , and part of it appears in the gap between the blocks of the block-like gC 3 N 4 .
实施例2：Example 2:
一种本发明的氮化碳-钛酸镍复合材料，包括氮化碳和钛酸镍，其中氮化碳为块状，钛酸镍为棒状，棒状的钛酸镍沉积于块状的氮化碳表面，其中氮化碳的质量分数为10%。A carbon nitride-nickel titanate composite material of the present invention comprises carbon nitride and nickel titanate, wherein the carbon nitride is block-shaped, nickel titanate is rod-shaped, and the rod-shaped nickel titanate is deposited on the block-shaped nitrided Carbon surface, wherein the mass fraction of carbon nitride is 10%.
一种上述本实施例的氮化碳-钛酸镍复合材料的制备方法，与实施例1的制备方法的区别仅在于步骤（1）中双氰胺用量为150mg，其余步骤均相同。A method for preparing the carbon nitride-nickel titanate composite material of the above-mentioned embodiment differs from the method of embodiment 1 only in that the amount of dicyandiamide in step (1) is 150 mg, and the rest of the steps are the same.
实施例3：Example 3:
一种本发明的氮化碳-钛酸镍复合材料，包括氮化碳和钛酸镍，其中氮化碳为块状，钛酸镍为棒状，棒状的钛酸镍沉积于块状的氮化碳表面，其中氮化碳的质量分数为27.3%。A carbon nitride-nickel titanate composite material of the present invention comprises carbon nitride and nickel titanate, wherein the carbon nitride is block-shaped, nickel titanate is rod-shaped, and the rod-shaped nickel titanate is deposited on the block-shaped nitrided Carbon surface, in which the mass fraction of carbon nitride is 27.3%.
一种上述本实施例的氮化碳-钛酸镍复合材料的制备方法，与实施例1的制备方法区别仅在于步骤（1）中双氰胺用量为500mg，其余步骤均相同。A method for preparing the carbon nitride-nickel titanate composite material of the above-mentioned embodiment differs from the method of embodiment 1 only in that the amount of dicyandiamide in step (1) is 500 mg, and the rest of the steps are the same.
分别对g-C3N4、NiTiO3以及实施例1～3的氮化碳-钛酸镍复合材料进行紫外-可见漫反射吸收光谱检测，图3为g-C3N4、NiTiO3以及实施例1～3的氮化碳-钛酸镍复合材料对应的紫外-可见漫反射吸收光谱图。从图中可以看出g-C3N4和NiTiO3在紫外以及可见区域都有很强的光吸收。实施例1～3的氮化碳-钛酸镍复合材料在可见光区域的光吸收均较NiTiO3在该区域的光吸收有所增强。The ultraviolet-visible diffuse reflectance absorption spectrum detection is carried out on gC 3 N 4 , NiTiO 3 and the carbon nitride-nickel titanate composite materials of Examples 1-3, and Fig. 3 shows gC 3 N 4 , NiTiO 3 and Examples 1-3 The UV-Vis diffuse reflectance absorption spectrum corresponding to the carbon nitride-nickel titanate composite material of 3. It can be seen from the figure that gC 3 N 4 and NiTiO 3 have strong light absorption in the ultraviolet and visible regions. The light absorption of the carbon nitride-nickel titanate composite materials in Examples 1 to 3 in the visible light region is stronger than that of NiTiO 3 in this region.
实施例4：Example 4:
一种实施例1的氮化碳-钛酸镍复合材料与g-C3N4、NiTiO3在降解废水中的硝基苯的效果对比，包括以下步骤：A kind of carbon nitride-nickel titanate composite material of embodiment 1 and gC 3 N 4 , NiTiO 3 Effect contrast in degrading the nitrobenzene in waste water, comprises the following steps:
（1）配制3组（组1、组2和组3）浓度为20mg/L的硝基苯溶液各100ml，并各加入2mL乙醇，将配制的溶液放于阴暗处。(1) Prepare 3 groups (group 1, group 2 and group 3) of 100ml of nitrobenzene solutions with a concentration of 20mg/L each, add 2mL of ethanol to each, and put the prepared solutions in a dark place.
（2）称取g-C3N4、NiTiO3和实施例1的氮化碳-钛酸镍复合材料各0.04g，将称取的g-C3N4加入到组1的硝基苯溶液中， NiTiO3加入到组2的硝基苯溶液中，氮化碳-钛酸镍复合材料加入到组3的硝基苯溶液中，均在暗处磁力搅拌一个小时达到吸附平衡。每组各取出4ml溶液来代表待降解的初始液，即反应时间为0min时的溶液，用紫外可见分光光度仪测其浓度，并记为C0。(2) Weigh 0.04g each of gC 3 N 4 , NiTiO 3 and the carbon nitride-nickel titanate composite material in Example 1, and add the weighed gC 3 N 4 to the nitrobenzene solution of Group 1. NiTiO 3 was added to the nitrobenzene solution of group 2, and the carbon nitride-nickel titanate composite material was added to the nitrobenzene solution of group 3, and both were magnetically stirred in the dark for one hour to reach adsorption equilibrium. Take out 4ml of solution from each group to represent the initial solution to be degraded, that is, the solution when the reaction time is 0min, measure its concentration with an ultraviolet-visible spectrophotometer, and record it as C 0 .
（3）将步骤（2）中3组剩余的溶液在可见光光源300W的氙灯照射下进行光催化反应并开始计时，光源与液面距离为15cm。(3) The remaining solutions of the three groups in step (2) were subjected to a photocatalytic reaction under the irradiation of a 300W xenon lamp with a visible light source, and the timing was started. The distance between the light source and the liquid surface was 15cm.
（4）每隔20min从每组的反应体系内各吸取4ml溶液，在7000转下离心5min后，吸取上清液，用紫外可见分光光度仪测上清液中染料残余浓度。待光照反应120min后，关闭氙灯。(4) Take 4ml of solution from the reaction system of each group every 20 minutes, centrifuge at 7000 rpm for 5 minutes, take out the supernatant, and measure the residual dye concentration in the supernatant with a UV-visible spectrophotometer. After 120 minutes of light reaction, turn off the xenon lamp.
图4为本发明中的氮化碳-钛酸镍复合材料光催化降解废水中的硝基苯的降解原理图。其中，e- 表示电子，h+ 表示空穴，H+ 表示还原氢离子。如图所示，当光照射于g-C3N4/NiTiO3复合材料后，g-C3N4中的电子激发跃迁到导带（CB），由于g-C3N4的导带位置比NiTiO3的导带位置更负，g-C3N4导带上的电子将转移到NiTiO3导带上并留下空穴。同时，产生的空穴从NiTiO3价带（VB）转移到g-C3N4价带。同时，乙醇消耗空穴，产生还原氢离子和乙醛，所以光生电子和氢离子将攻击那些吸附在光催化剂表面的硝基苯使其降解。Fig. 4 is a schematic diagram of the photocatalytic degradation of nitrobenzene in waste water by the carbon nitride-nickel titanate composite material in the present invention. Among them, e - means electron, h + means hole, H + means reduced hydrogen ion. As shown in the figure, when light is irradiated on the gC 3 N 4 /NiTiO 3 composite, the electrons in gC 3 N 4 are excited and transition to the conduction band (CB), because the conduction band position of gC 3 N 4 is higher than that of NiTiO 3 The band position is more negative, the electrons on the conduction band of gC3N4 will transfer to the conduction band of NiTiO3 and leave holes. At the same time, the generated holes are transferred from the NiTiO 3 valence band (VB) to the gC 3 N 4 valence band. At the same time, ethanol consumes holes and produces reduced hydrogen ions and acetaldehyde, so photogenerated electrons and hydrogen ions will attack those nitrobenzene adsorbed on the surface of the photocatalyst to degrade them.
图5是g-C3N4、NiTiO3以及本发明实施例1中的氮化碳-钛酸镍复合材料光催化降解废水中的硝基苯对应的时间-降解效率的关系图。其中C代表降解后的硝基苯的残余浓度，C0表示硝基苯初始浓度。以C/C0为纵坐标，以光照时间为横坐标，g-C3N4，NiTiO3以及本发明实施例1中的氮化碳-钛酸镍复合材料的光催化性能曲线如图5示。由图可知，可见光照射120min后，g-C3N4对硝基苯降解效率仅为56%，NiTiO3对硝基苯降解效率仅为62%，而本发明实施例1中的氮化碳-钛酸镍复合材料对硝基苯降解效率达到80%，明显高于单体对硝基苯的降解率。这表明，本发明的氮化碳-钛酸镍复合材料具有很强的光催化活性。Fig. 5 is a time-degradation efficiency relation diagram corresponding to the photocatalytic degradation of nitrobenzene in waste water by gC 3 N 4 , NiTiO 3 and the carbon nitride-nickel titanate composite material in Example 1 of the present invention. where C represents the residual concentration of nitrobenzene after degradation, and C represents the initial concentration of nitrobenzene. With C/C 0 as the ordinate and light time as the abscissa, the photocatalytic performance curves of gC 3 N 4 , NiTiO 3 and the carbon nitride-nickel titanate composite material in Example 1 of the present invention are shown in FIG. 5 . It can be seen from the figure that after 120 min of visible light irradiation, the degradation efficiency of gC 3 N 4 p-nitrobenzene is only 56%, and the degradation efficiency of NiTiO 3 p-nitrobenzene is only 62%, while the carbon nitride-titanium in Example 1 of the present invention The degradation efficiency of p-nitrobenzene of nickel acid composite material reaches 80%, which is obviously higher than that of monomer p-nitrobenzene. This shows that the carbon nitride-nickel titanate composite material of the present invention has strong photocatalytic activity.
实施例5：Example 5:
一种实施例1～3的氮化碳-钛酸镍复合材料在硝基苯废水处理中的应用，包括以下步骤：An application of the carbon nitride-nickel titanate composite material of embodiments 1 to 3 in the treatment of nitrobenzene wastewater comprises the following steps:
（1）取3组（组1、组2和组3）含硝基苯和乙醇的染料废水，每组中硝基苯的浓度为20mg/L，乙醇的添加量为2v/v %。按照用量为0.4g/L在组1的染料废水中添加实施例1的氮化碳-钛酸镍复合材料，按照用量为0.4g/L在组2的染料废水中添加实施例2的氮化碳-钛酸镍复合材料，按照用量为0.4g/L在组3的染料废水中添加实施例3的氮化碳-钛酸镍复合材料。实施例1～3中g-C3N4的质量百分含量分别约为18.4%、10%和27.3%，依次编号为g-C3N4/NiTiO3-18.4%，g-C3N4/NiTiO3-10%，g-C3N4/NiTiO3-27.3%。(1) Take 3 groups (group 1, group 2 and group 3) of dye wastewater containing nitrobenzene and ethanol, the concentration of nitrobenzene in each group is 20mg/L, and the amount of ethanol added is 2v/v%. Add the carbon nitride-nickel titanate composite material of Example 1 to the dye wastewater of Group 1 according to the dosage of 0.4g/L, and add the nitriding compound of Example 2 to the dye wastewater of Group 2 according to the dosage of 0.4g/L. For the carbon-nickel titanate composite material, the carbon nitride-nickel titanate composite material of Example 3 was added to the dye wastewater of Group 3 according to the dosage of 0.4g/L. The mass percentages of gC 3 N 4 in Examples 1 to 3 are about 18.4%, 10% and 27.3% respectively, which are sequentially numbered as gC 3 N 4 /NiTiO 3 -18.4%, gC 3 N 4 /NiTiO 3 -10 %, gC 3 N 4 /NiTiO 3 -27.3%.
（2）将每组的反应***（添加有氮化碳-钛酸镍复合材料的含硝基苯的废水）置于磁力搅拌器上，避光搅拌1h，使氮化碳-钛酸镍复合材料与污染物废水达到吸附平衡，从3组中分别取出4ml溶液来代表各组待降解的初始液，即反应时间为0min时的溶液，用紫外可见分光光度仪测其浓度，并记为C0。(2) Put the reaction system of each group (nitrobenzene-containing wastewater added with carbon nitride-nickel titanate composite material) on a magnetic stirrer, and stir for 1 hour in the dark to make the carbon nitride-nickel titanate composite The material and the pollutant wastewater reached adsorption equilibrium, and 4ml of the solution was taken out from the three groups to represent the initial solution to be degraded in each group, that is, the solution when the reaction time was 0min, and its concentration was measured by a UV-visible spectrophotometer, and recorded as C 0 .
（3）将步骤（2）中3组剩余的溶液在可见光光源300W的氙灯照射下进行光催化反应并开始计时，光源与液面距离为15cm。每隔20min从每组的反应体系内各吸取4ml溶液，在7000转下离心5min后，吸取上清液，用紫外可见分光光度仪测上清液中染料残余浓度。待光照反应120min后，关闭氙灯。(3) The remaining solutions of the three groups in step (2) were subjected to a photocatalytic reaction under the irradiation of a 300W xenon lamp with a visible light source, and the timing was started. The distance between the light source and the liquid surface was 15cm. Draw 4ml of solution from the reaction system of each group every 20min, centrifuge at 7000 rpm for 5min, draw the supernatant, and measure the residual dye concentration in the supernatant with a UV-visible spectrophotometer. After 120 minutes of light reaction, turn off the xenon lamp.
图6是本发明实施例1～3的氮化碳-钛酸镍复合材料在可见光下还原硝基苯的性能曲线。其中C代表降解后的硝基苯的浓度，C0表示硝基苯初始浓度。以C/C0为纵坐标，以光照时间为横坐标。由图可见，随着g-C3N4在氮化碳-钛酸镍复合材料中的比重从零开始逐渐增加，氮化碳-钛酸镍复合材料对硝基苯降解效率随之增强，当g-C3N4的比重增加到22%时，氮化碳-钛酸镍复合材料对硝基苯降解效率达到最大值80%。而当g-C3N4比重继续增加时，氮化碳-钛酸镍复合材料对硝基苯降解效率逐渐降低。实施例2的氮化碳-钛酸镍复合材料（g-C3N4/NiTiO3-10%）、实施例1的氮化碳-钛酸镍复合材料（g-C3N4/NiTiO3-18.4%）和实施例3的氮化碳-钛酸镍复合材料（g-C3N4/NiTiO3-27.3%）对硝基苯降解效率分别为76%、80%和67%。通过该图可以看出，实施例1的氮化碳-钛酸镍复合材料（g-C3N4/NiTiO3-18.4%）对硝基苯的光催化降解效果最佳。Fig. 6 is a performance curve of the carbon nitride-nickel titanate composite material of Examples 1-3 of the present invention for reducing nitrobenzene under visible light. where C represents the concentration of degraded nitrobenzene, and C0 represents the initial concentration of nitrobenzene. Take C/C 0 as the ordinate, and the light time as the abscissa. It can be seen from the figure that as the proportion of gC 3 N 4 in the carbon nitride-nickel titanate composite material gradually increases from zero, the degradation efficiency of nitrobenzene in the carbon nitride-nickel titanate composite material increases accordingly. When gC When the specific gravity of 3 N 4 increased to 22%, the degradation efficiency of carbon nitride-nickel titanate composites reached a maximum of 80%. When the specific gravity of gC 3 N 4 continued to increase, the degradation efficiency of carbon nitride-nickel titanate composites decreased gradually. The carbon nitride-nickel titanate composite material of Example 2 (gC 3 N 4 /NiTiO 3 -10%), the carbon nitride-nickel titanate composite material of Example 1 (gC 3 N 4 /NiTiO 3 -18.4% ) and the carbon nitride-nickel titanate composite material (gC 3 N 4 /NiTiO 3 -27.3%) of Example 3 had a p-nitrobenzene degradation efficiency of 76%, 80% and 67%, respectively. It can be seen from the figure that the carbon nitride-nickel titanate composite material (gC 3 N 4 /NiTiO 3 -18.4%) in Example 1 has the best photocatalytic degradation effect on nitrobenzene.
实施例6：Embodiment 6:
一种本发明的氮化碳-钛酸镍复合材料在光催化降解过程中的抗腐蚀性和稳定性研究，包括以下步骤：A kind of corrosion resistance and stability research of carbon nitride-nickel titanate composite material of the present invention in photocatalytic degradation process, comprises the following steps:
（1）称取40mg实施例1的氮化碳-钛酸镍复合材料，添加至100ml含硝基苯的废水中，硝基苯浓度为20mg/L，并加入2mL的无水乙醇。(1) Weigh 40 mg of the carbon nitride-nickel titanate composite material of Example 1, add it to 100 ml of wastewater containing nitrobenzene, the concentration of nitrobenzene is 20 mg/L, and add 2 mL of absolute ethanol.
（2）将反应体系（添加有氮化碳-钛酸镍复合材料的含硝基苯的废水）置于磁力搅拌器上，避光搅拌1h以达到吸附平衡，从中取出4ml溶液来代表待降解的初始液，即反应时间为0min时的溶液，用紫外可见分光光度仪测其浓度，并记为C0。(2) Put the reaction system (nitrobenzene-containing wastewater added with carbon nitride-nickel titanate composite material) on a magnetic stirrer, and stir for 1 hour in the dark to achieve adsorption equilibrium, and take 4ml of the solution to represent the solution to be degraded The initial solution, that is, the solution when the reaction time is 0 min, its concentration was measured with a UV-visible spectrophotometer, and recorded as C 0 .
（3）将步骤（2）剩余的溶液在可见光光源300W的氙灯下进行光催化反应并开始计时，光源与液面距离为15cm。每隔20min从反应体系内取4ml溶液离心分离，用紫外可见分光光度仪测上清液中硝基苯残余浓度，记为C。待光照反应120min后，关闭氙灯。(3) The remaining solution in step (2) was subjected to a photocatalytic reaction under a 300W xenon lamp with a visible light source, and the timing was started. The distance between the light source and the liquid surface was 15cm. Take 4ml of the solution from the reaction system every 20min and centrifuge, measure the residual concentration of nitrobenzene in the supernatant with a UV-visible spectrophotometer, and record it as C. After 120 minutes of light reaction, turn off the xenon lamp.
（4）将步骤（3）反应后的溶液离心分离，用紫外可见分光光度仪测上清液中污染物残余浓度并计算降解效率。倒掉上清液，收集反应后的氮化碳-钛酸镍复合材料，并重新加入到100ml硝基苯浓度为20mg/L的废水中。(4) Centrifuge the solution after the reaction in step (3), measure the residual concentration of pollutants in the supernatant with an ultraviolet-visible spectrophotometer and calculate the degradation efficiency. Pour off the supernatant, collect the reacted carbon nitride-nickel titanate composite material, and re-add it to 100ml of wastewater with a nitrobenzene concentration of 20mg/L.
（5）继续重复步骤（2）～（4）四次。(5) Continue to repeat steps (2) to (4) four times.
图7是本发明实施例1的氮化碳-钛酸镍复合材料循环反应五次的光催化性能曲线。以硝基苯的的降解效率为纵坐标，以循环次数为横坐标，由图可以看出，经过五次循环后，氮化碳-钛酸镍复合材料依然展现出高效的光催化性能，五次循环的降解效率依次为80%，79.3%，78.6%，77.8%和77.3%。由此说明氮化碳-钛酸镍复合材料是一种稳定且高效的新型复合光催化剂，具有很好的实际应用前景。Fig. 7 is the photocatalytic performance curve of the carbon nitride-nickel titanate composite material in Example 1 of the present invention after five cycles of reaction. Taking the degradation efficiency of nitrobenzene as the ordinate and the number of cycles as the abscissa, it can be seen from the figure that after five cycles, the carbon nitride-nickel titanate composite still exhibits high-efficiency photocatalytic performance. The degradation efficiencies of the secondary cycles were 80%, 79.3%, 78.6%, 77.8% and 77.3%. This shows that the carbon nitride-nickel titanate composite material is a stable and efficient new composite photocatalyst, which has a good prospect for practical application.
以上所述仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例。凡属于本发明思路下的技术方案均属于本发明的保护范围。应该指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下的改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above descriptions are only preferred implementations of the present invention, and the scope of protection of the present invention is not limited to the above examples. All technical solutions under the idea of the present invention belong to the protection scope of the present invention. It should be pointed out that for those skilled in the art, improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.
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