CN111841525B - Graphene oxide-based photocatalyst with visible light response and preparation method thereof - Google Patents
Graphene oxide-based photocatalyst with visible light response and preparation method thereof Download PDFInfo
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Abstract
Description
技术领域technical field
本发明涉及光催化剂技术领域，更具体地，涉及一种具有可见光响应的氧化石墨烯基光催化剂及其制备方法。The invention relates to the technical field of photocatalysts, in particular to a graphene oxide-based photocatalyst with visible light response and a preparation method thereof.
背景技术Background technique
近年来，环境污染事件频频发生，已成为全球关注的环境问题。光催化氧化技术可以利用光照来催生光催化反应生成一系列具有高活性的强氧化剂，进而绿色有效的将各种有机污染物降解成无毒的物质。因而半导体光催化氧化技术被认为是最有前途的一种净化方法。拓展光催化材料的光谱响应范围、提高光催化反应速率和量子效率等一直是半导体光催化技术研究的重点。In recent years, environmental pollution incidents have occurred frequently, which has become an environmental issue of global concern. Photocatalytic oxidation technology can use light to catalyze photocatalytic reactions to generate a series of highly active and strong oxidants, and then green and effectively degrade various organic pollutants into non-toxic substances. Therefore, semiconductor photocatalytic oxidation technology is considered to be the most promising purification method. Expanding the spectral response range of photocatalytic materials, improving the photocatalytic reaction rate and quantum efficiency have always been the focus of semiconductor photocatalytic technology research.
在光催化研究领域中，目前实际使用中较广泛的是商业纳米二氧化钛粉末(P25)，它独特的光化学性能已使其可用于许多领域，如空气、水和流体的净化。以碳或其他杂原子掺杂的光催化剂也可用于具有散射光源的密封空间或区域。用于建筑、人行石板、混凝土墙或屋顶瓦上的涂料中时，它们可以明显增加对空气中污染物如氮氧化物、芳烃和醛类的分解。In the field of photocatalytic research, the commercial nano-titanium dioxide powder (P25) is currently widely used in practice. Its unique photochemical properties have made it applicable to many fields, such as air, water and fluid purification. Photocatalysts doped with carbon or other heteroatoms can also be used in enclosed spaces or areas with diffuse light sources. When used in coatings on buildings, pavement slabs, concrete walls or roof tiles, they can significantly increase the breakdown of airborne pollutants such as nitrogen oxides, aromatics and aldehydes.
但二氧化钛粉末禁带宽度较宽(Eg＝3.2eV)，只能被紫外光激发，对太阳光利用率很低，且粒径相对较大，比表面积也小，纳米材料特性不显著。另外，光激发产生的电子和空穴对易复合，光量子效率低。同时TiO2的带隙较宽，仅对紫外光有相应，对可见光的利用率不高。现有技术中制备的具有可见光响应的氧化石墨烯-铈-二氧化钛(GO-Ce-TiO2)粉体型光催化剂，虽然拓展了光谱响应范围，但是光催化反应速度和效率仍有待提高。However, titanium dioxide powder has a wide band gap (Eg=3.2eV), can only be excited by ultraviolet light, has a low utilization rate of sunlight, and has relatively large particle size and small specific surface area, so the characteristics of nanomaterials are not significant. In addition, the electron and hole pairs generated by photoexcitation are easy to recombine, and the photon quantum efficiency is low. At the same time, TiO 2 has a wide band gap, which only responds to ultraviolet light, and the utilization rate of visible light is not high. The graphene oxide-cerium-titanium dioxide (GO-Ce-TiO 2 ) powder photocatalyst with visible light response prepared in the prior art has expanded the spectral response range, but the photocatalytic reaction speed and efficiency still need to be improved.
发明内容Contents of the invention
本发明的目的在于针对现有技术中的不足，提供一种具有可见光响应的氧化石墨烯基光催化剂的制备方法，基于氧化石墨烯(GO)的大的比表面积和支撑作用，结合TiO2的光催化性和La离子的拓展光谱的能力，采用一步溶胶凝胶法使三者键合，制备工艺简单。The purpose of the present invention is to address the deficiencies in the prior art, to provide a method for preparing a graphene oxide-based photocatalyst with visible light response, based on the large specific surface area and supporting effect of graphene oxide (GO), combined with TiO2 Photocatalysis and the ability to expand the spectrum of La ions are bonded by a one-step sol-gel method, and the preparation process is simple.
本发明的另一目的在于提供上述制备方法得到的具有可见光响应的氧化石墨烯基光催化剂。Another object of the present invention is to provide a graphene oxide-based photocatalyst with visible light response obtained by the above preparation method.
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:
一种具有可见光响应的氧化石墨烯基光催化剂的制备方法，包括以下步骤：A preparation method of a graphene oxide-based photocatalyst with visible light response, comprising the following steps:
S1.将氧化石墨烯溶解至无水乙醇溶液中，经超声处理得氧化石墨烯悬浮液，搅拌均匀，向氧化石墨烯悬浮液中添加冰醋酸调节pH，然后逐滴加入钛酸四丁酯并持续搅拌；S1. Dissolve graphene oxide in absolute ethanol solution, obtain graphene oxide suspension through ultrasonic treatment, stir evenly, add glacial acetic acid to adjust pH in graphene oxide suspension, then add tetrabutyl titanate dropwise and keep stirring;
S2.向氧化石墨烯悬浮液中加入混合溶液和硝酸镧，所述混合溶液包括无水乙醇、冰醋酸、超纯水，持续搅拌后得La-GO-TiO2溶胶；S2. Add mixed solution and lanthanum nitrate in graphene oxide suspension, described mixed solution comprises dehydrated alcohol, glacial acetic acid, ultrapure water, obtains La-GO- TiO after continuous stirring sol;
S3.将La-GO-TiO2溶胶陈化至凝胶状态，然后经干燥、研磨和煅烧，得La-GO-TiO2催化剂粉体。S3. Aging the La-GO-TiO 2 sol to a gel state, and then drying, grinding and calcining to obtain a La-GO-TiO 2 catalyst powder.
进一步地，步骤S1中所述无水乙醇溶液、冰醋酸和钛酸四丁酯的体积比为30～35:4～6:5～8。Further, the volume ratio of the absolute ethanol solution, glacial acetic acid and tetrabutyl titanate in step S1 is 30-35:4-6:5-8.
进一步地，步骤S1中所述氧化石墨烯悬浮液中氧化石墨烯的浓度为0.1～0.7mg/ml。Further, the concentration of graphene oxide in the graphene oxide suspension in step S1 is 0.1-0.7 mg/ml.
进一步地，步骤S2中所述混合溶液的添加量为4ml，所述硝酸镧的添加量为0.03～0.3g。Further, the added amount of the mixed solution in step S2 is 4ml, and the added amount of the lanthanum nitrate is 0.03-0.3g.
进一步地，步骤S2中所述混合溶液中无水乙醇、冰醋酸和超纯水的体积比为：4:5:1。Further, the volume ratio of absolute ethanol, glacial acetic acid and ultrapure water in the mixed solution in step S2 is: 4:5:1.
进一步地，步骤S1中所述搅拌时间为1h，步骤S2中所述搅拌时间为3h。Further, the stirring time in step S1 is 1 h, and the stirring time in step S2 is 3 h.
进一步地，步骤S3中所述陈化时间为1d。Further, the aging time in step S3 is 1d.
进一步地，步骤S3中所述干燥过程在真空干燥箱中进行，干燥温度为45℃。Further, the drying process in step S3 is carried out in a vacuum drying oven at a drying temperature of 45°C.
进一步地，步骤S3中所述煅烧过程在氮气氛围下的管式炉中进行，烧结温度为200～500℃、时间为2.5h。Further, the calcination process in step S3 is carried out in a tube furnace under nitrogen atmosphere, the sintering temperature is 200-500°C, and the sintering time is 2.5h.
一种根据上述制备方法得到的具有可见光效应的氧化石墨烯基光催化剂。A graphene oxide-based photocatalyst with visible light effect obtained according to the above preparation method.
与现有技术相比，本发明的有益效果如下：Compared with the prior art, the beneficial effects of the present invention are as follows:
本发明以氧化石墨烯为载体，在氧化石墨烯片层上分布有活性氧官能团和缺陷，有利于结合La和TiO2，提高光催化剂的催化效率。本发明制备的光催化剂中La离子的半径(106pm)大于TiO2中Ti离子的半径(68pm)，当La掺杂代替Ti原子时，会导致TiO2晶格畸变产生内部偶极矩，有利于电子-空穴对的分离，并且La掺杂TiO2后，La 5d电子态的引入使得Ti3d与La 5d电子态之间发生相互作用，导致导带向低能端运动，使其带隙减小从而将TiO2的吸收光谱扩展到可见光区域。The invention uses graphene oxide as a carrier, and active oxygen functional groups and defects are distributed on the graphene oxide sheet, which is beneficial for combining La and TiO 2 and improving the catalytic efficiency of the photocatalyst. The radius (106pm) of La ion in the photocatalyst prepared by the present invention is greater than the radius (68pm) of Ti ion in TiO2 , when La doping replaces Ti atom, can cause TiO2Lattice distortion produces internal dipole moment, is conducive to The separation of electron-hole pairs, and the introduction of La 5d electronic state after La doping TiO 2 makes the interaction between Ti3d and La 5d electronic state cause the conduction band to move to the lower energy end, reducing its band gap and thus Extend the absorption spectrum of TiO2 to the visible region.
本发明制备的氧化石墨烯基光催化剂具有良好的可见光光催化活性，GO、La和TiO2间具有明显的协同作用，氧化石墨烯的大比表面积能更多的吸附有机污染物，氧化石墨烯极强的导电能力和La的缩小带隙的能力，能有效地抑制电子-空穴对的复合，促进光催化剂的光催化降解能力，使其吸收波长的边界红移到了580nm，极大地提高对可见光的吸收利用。The graphene oxide-based photocatalyst prepared by the present invention has good visible light photocatalytic activity, and there is an obvious synergistic effect between GO, La and TiO2 . The large specific surface area of graphene oxide can adsorb more organic pollutants, and graphene oxide The extremely strong conductivity and the ability of La to narrow the bandgap can effectively inhibit the recombination of electron-hole pairs, promote the photocatalytic degradation ability of photocatalysts, and redshift the boundary of the absorption wavelength to 580nm, which greatly improves the photocatalyst. Absorption of visible light.
附图说明Description of drawings
图1为La-GO-TiO2粉体的紫外可见光谱图；Fig. 1 is La-GO- TiO The ultraviolet-visible spectrogram of powder;
图2为亚甲基蓝的光催化降解实验示意图；Fig. 2 is the schematic diagram of the photocatalytic degradation experiment of methylene blue;
图3为光催化剂对对亚甲基蓝的光降解图。Fig. 3 is the photodegradation diagram of photocatalyst to p-methylene blue.
其中，1为氙灯、2为烧杯、3为磁力转子、4为磁力搅拌器。Among them, 1 is a xenon lamp, 2 is a beaker, 3 is a magnetic rotor, and 4 is a magnetic stirrer.
具体实施方式Detailed ways
为了便于理解本发明，下文将结合实施例对本发明作更全面、细致地描述，但本发明的保护范围并不限于以下具体的实施例。In order to facilitate the understanding of the present invention, the present invention will be described more fully and in detail below in conjunction with examples, but the protection scope of the present invention is not limited to the following specific examples.
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解的含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不旨在限制本发明的保护范围。Unless otherwise defined, all technical terms used hereinafter have the same meanings as commonly understood by those skilled in the art. The terminology used herein is only for the purpose of describing specific embodiments, and is not intended to limit the protection scope of the present invention.
除非另有特别说明，本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.
本发明制所用的氧化石墨烯基于改进的Hummers法从膨胀石墨中制备而成，具体地，氧化石墨烯的制备方法如下：The graphene oxide used in the present invention is prepared from expanded graphite based on the improved Hummers method. Specifically, the graphene oxide preparation method is as follows:
Y1.将装有23mL浓硫酸的容器置于0℃的冰水浴中，再向其缓慢加入1.0g可膨胀石墨和0.5g硝酸钠，开启超声振荡1h并控制反应液温度在4℃左右。然后将容器转入磁力搅拌器中，并在搅拌过程中逐步加入3g高锰酸钾，使混合物的温度保持在10℃以下并保持搅拌2h；Y1. Place the container containing 23mL of concentrated sulfuric acid in an ice-water bath at 0°C, then slowly add 1.0g of expandable graphite and 0.5g of sodium nitrate to it, turn on ultrasonic oscillation for 1 hour and control the temperature of the reaction solution at about 4°C. Then the container was transferred to a magnetic stirrer, and 3 g of potassium permanganate was gradually added during the stirring process, so that the temperature of the mixture was kept below 10° C. and kept stirring for 2 h;
Y2.将容器转移至超声波清洗机的水浴中，在35℃左右的条件下超声30min；Y2. Transfer the container to the water bath of the ultrasonic cleaner, and ultrasonicate for 30 minutes at about 35°C;
Y3.再将100mL超纯水缓缓加入到上述混合溶液中，中速搅拌条件下保持水浴温度在98℃左右15min；Y3. Slowly add 100mL of ultrapure water into the above mixed solution, and keep the water bath temperature at about 98°C for 15min under medium-speed stirring;
Y4.加入60mL超纯水后再加入25mL30％的双氧水终止反应过程，此时溶液呈现金黄色。陈放一段时间后，倒去上层的清液，最后用5％盐酸和超纯水充分洗涤棕黄色沉淀物至中性，并用氯化钡溶液检测离心后上层滤液里有无硫酸根离子存在，没有即可停止洗涤。即可通过离心和洗涤得到固体产品，将该固态产品放于50℃真空干燥箱中烘干，得氧化石墨烯。Y4. After adding 60mL of ultrapure water, add 25mL of 30% hydrogen peroxide to terminate the reaction process. At this time, the solution is golden yellow. After aging for a period of time, pour off the supernatant liquid, and finally wash the brownish-yellow precipitate with 5% hydrochloric acid and ultrapure water to neutrality, and use barium chloride solution to detect whether there is sulfate ion in the supernatant filtrate after centrifugation. to stop washing. A solid product can be obtained by centrifugation and washing, and the solid product is dried in a vacuum oven at 50° C. to obtain graphene oxide.
实施例1Example 1
本实施例提供一种具有可见光响应的氧化石墨烯基光催化剂的制备方法，具体包括以下步骤：This embodiment provides a method for preparing a graphene oxide-based photocatalyst with visible light response, which specifically includes the following steps:
S1.将10mg氧化石墨烯溶解至30ml无水乙醇溶液中，超声处理1h后得氧化石墨烯悬浮液，然后转移到磁力搅拌器中，搅拌1h；向氧化石墨烯悬浮液中添加4ml冰醋酸调节pH至5～6，然后逐滴加入5ml钛酸四丁酯并持续搅拌1h；S1. Dissolve 10mg of graphene oxide into 30ml of absolute ethanol solution, sonicate for 1h to obtain a graphene oxide suspension, then transfer to a magnetic stirrer, and stir for 1h; add 4ml of glacial acetic acid to the graphene oxide suspension to adjust pH to 5-6, then add 5ml tetrabutyl titanate dropwise and keep stirring for 1h;
S2.向氧化石墨烯悬浮液中加入混合溶液和硝酸镧，其中混合溶液由无水乙醇、冰醋酸、超纯水按体积比：4:5:1配制而成，混合溶液的加入量为4ml，硝酸镧的加入量为0.03g，持续搅拌3h后得La-GO-TiO2溶胶；S2. Add mixed solution and lanthanum nitrate to graphene oxide suspension, wherein mixed solution is formulated by volume ratio: 4:5:1 by absolute ethanol, glacial acetic acid, ultrapure water, the addition of mixed solution is 4ml , the addition of lanthanum nitrate is 0.03g, after continuous stirring for 3h, La-GO- TiO sol is obtained;
S3.将La-GO-TiO2溶胶陈化1d至凝胶状态，然后置于45℃的真空干燥箱中干燥，研磨后放入氮气氛围下的管式炉中进行煅烧，煅烧温度为350℃，时间为2.5h，得La-GO-TiO2催化剂粉体。S3. Aging the La-GO-TiO 2 sol for 1d to a gel state, then drying it in a vacuum oven at 45°C, grinding it and putting it into a tube furnace under a nitrogen atmosphere for calcination at a temperature of 350°C , the time is 2.5h, and the La-GO-TiO 2 catalyst powder is obtained.
实施例2Example 2
本实施例提供一种具有可见光响应的氧化石墨烯基光催化剂的制备方法，具体包括以下步骤：This embodiment provides a method for preparing a graphene oxide-based photocatalyst with visible light response, which specifically includes the following steps:
S1.将5mg氧化石墨烯溶解至35ml无水乙醇溶液中，超声处理1h后得氧化石墨烯悬浮液，然后转移到磁力搅拌器中，搅拌1h；向氧化石墨烯悬浮液中添加4ml冰醋酸调节pH至5～6，然后逐滴加入8ml钛酸四丁酯并持续搅拌1h；S1. Dissolve 5mg of graphene oxide into 35ml of absolute ethanol solution, sonicate for 1h to obtain a graphene oxide suspension, then transfer to a magnetic stirrer, and stir for 1h; add 4ml of glacial acetic acid to the graphene oxide suspension to adjust pH to 5-6, then add 8ml tetrabutyl titanate dropwise and keep stirring for 1h;
S2.向氧化石墨烯悬浮液中加入混合溶液和硝酸镧，其中混合溶液由无水乙醇、冰醋酸、超纯水按体积比：4:5:1配制而成，混合溶液的加入量为4ml，硝酸镧的加入量为0.3g，持续搅拌3h后得La-GO-TiO2溶胶；S2. Add mixed solution and lanthanum nitrate to graphene oxide suspension, wherein mixed solution is formulated by volume ratio: 4:5:1 by absolute ethanol, glacial acetic acid, ultrapure water, the addition of mixed solution is 4ml , the addition of lanthanum nitrate is 0.3g, after continuous stirring for 3h, La-GO- TiO sol is obtained;
S3.将La-GO-TiO2溶胶陈化1d至凝胶状态，然后置于45℃的真空干燥箱中干燥，研磨后放入氮气氛围下的管式炉中进行煅烧，煅烧温度为200℃，时间为2.5h，得La-GO-TiO2催化剂粉体。S3. Aging the La-GO-TiO 2 sol for 1d to a gel state, then drying it in a vacuum oven at 45°C, grinding it and putting it into a tube furnace under a nitrogen atmosphere for calcination, the calcination temperature is 200°C , the time is 2.5h, and the La-GO-TiO 2 catalyst powder is obtained.
实施例3Example 3
S1.将20mg氧化石墨烯溶解至30ml无水乙醇溶液中，超声处理1h后得氧化石墨烯悬浮液，然后转移到磁力搅拌器中，搅拌1h；向氧化石墨烯悬浮液中添加6ml冰醋酸调节pH至5～6，然后逐滴加入5ml钛酸四丁酯并持续搅拌1h；S1. Dissolve 20mg of graphene oxide into 30ml of absolute ethanol solution, and obtain a graphene oxide suspension after ultrasonic treatment for 1h, then transfer it to a magnetic stirrer and stir for 1h; add 6ml of glacial acetic acid to the graphene oxide suspension to adjust pH to 5-6, then add 5ml tetrabutyl titanate dropwise and keep stirring for 1h;
S2.向氧化石墨烯悬浮液中加入混合溶液和硝酸镧，其中混合溶液由无水乙醇、冰醋酸、超纯水按体积比：4:5:1配制而成，混合溶液的加入量为4ml，硝酸镧的加入量为0.1g，持续搅拌3h后得Ce-GO-TiO2溶胶；S2. Add mixed solution and lanthanum nitrate to graphene oxide suspension, wherein mixed solution is formulated by volume ratio: 4:5:1 by absolute ethanol, glacial acetic acid, ultrapure water, the addition of mixed solution is 4ml , the addition of lanthanum nitrate is 0.1g, after continuous stirring for 3h, Ce-GO- TiO sol is obtained;
S3.将La-GO-TiO2溶胶陈化1d至凝胶状态，然后置于45℃的真空干燥箱中干燥，研磨后放入氮气氛围下的管式炉中进行煅烧，煅烧温度为500℃，时间为2.5h，得La-GO-TiO2催化剂粉体。S3. Aging the La-GO-TiO 2 sol for 1d to a gel state, then drying it in a vacuum oven at 45°C, grinding it and putting it into a tube furnace under a nitrogen atmosphere for calcination, the calcination temperature is 500°C , the time is 2.5h, and the La-GO-TiO 2 catalyst powder is obtained.
对比例1Comparative example 1
本对比例参照实施例1，提供一种TiO2光催化剂粉体的制备方法，与实施例不同之处在于：步骤S1中未加入氧化石墨烯，步骤S2中未加入硝酸镧。具体地，制备方法如下：This comparative example provides a preparation method of TiO2 photocatalyst powder with reference to Example 1. The difference from the Example is that no graphene oxide is added in step S1, and no lanthanum nitrate is added in step S2. Specifically, the preparation method is as follows:
S1.向30mL无水乙醇溶液中添加4mL冰醋酸，搅拌均匀调节pH至5～6，然后逐滴加入5mL的钛酸四丁酯并持续搅拌1h，S1. Add 4 mL of glacial acetic acid to 30 mL of absolute ethanol solution, stir evenly to adjust the pH to 5-6, then add 5 mL of tetrabutyl titanate dropwise and continue stirring for 1 h.
S2.逐滴加入4mL混合溶液，混合溶液由无水乙醇、冰醋酸、超纯水按体积比：4:5:1配制而成，持续搅拌3h后得到TiO2溶胶；S2. Add 4mL mixed solution dropwise, the mixed solution is prepared from absolute ethanol, glacial acetic acid, and ultrapure water in a volume ratio of 4:5:1, and the TiO sol is obtained after continuous stirring for 3 hours;
S3.再陈化1d到凝胶状态并置于45℃的真空干燥箱中。最后该固体经过研磨和350℃煅烧2.5h得到TiO2的催化剂粉体。S3. Aging for another 1d to a gel state and placed in a vacuum oven at 45°C. Finally, the solid was ground and calcined at 350° C. for 2.5 h to obtain TiO 2 catalyst powder.
对比例2Comparative example 2
本对比例参照实施例1，提供一种GO-TiO2光催化剂粉体的制备方法，与实施例1不同之处在于，步骤S2中未加入硝酸镧，其余工艺参数保持不变。This comparative example provides a preparation method of GO- TiO2 photocatalyst powder with reference to Example 1. The difference from Example 1 is that no lanthanum nitrate is added in step S2, and other process parameters remain unchanged.
对比例3Comparative example 3
本对比例参照实施例1，提供一种Ce-GO-TiO2光催化剂粉体的制备方法，与实施例1不同之处在于，步骤S2中使用硝酸铈代替硝酸镧，其余工艺参数保持不变。With reference to Example 1, this comparative example provides a method for preparing Ce-GO- TiO2 photocatalyst powder. The difference from Example 1 is that cerium nitrate is used instead of lanthanum nitrate in step S2, and the remaining process parameters remain unchanged. .
实施例1和对比例1～3制备的光催化剂粉体的的结构和光学特性如表1所示。The structures and optical properties of the photocatalyst powders prepared in Example 1 and Comparative Examples 1-3 are shown in Table 1.
表1Table 1
图1为实施例1和对比例1～3制备的光催化剂粉体的紫外可见光漫反射谱图。由图1可知，与TiO2相比，GO-TiO2的光吸收能力因为GO的存在而得到了明显的加强。但GO-TiO2和TiO2的吸收边界局限在紫外光区域，而La-GO-TiO2和Ce-GO-TiO2的吸收阀值却扩展至了可见光范围，这证明La或Ce的掺杂能将对可见光不响应的催化剂转变成可利用可见光源的光催化剂。La离子的半径(106pm)大于Ce离子的半径(103pm)，所以当掺杂TiO2时，La离子相比Ce离子更易引起TiO2晶体的形变，从而减小载流子的复合速率。La 5d电子态相比Ce 4f电子态，与Ti 3d电子态相互作用时更有利于带隙减小和电子的跃迁，使其吸收光谱发生红移。禁带宽度(Eg)可以通过公式计算得到，Eg＝1239.8/λ，其中λ(nm)是光谱吸收边界的波长。单掺杂GO、共掺杂Ce-GO和共掺杂La-GO的TiO2的禁带宽度分别是2.71、2.41和2.14eV(表1)。在氮气氛围下煅烧得到的La-GO-TiO2光催化剂，可以减少煅烧过程中GO的损失。La取代Ce后的禁带宽度从2.41eV下降到了2.14eV；结合图1看，La-GO-TiO2的吸收光谱的与Ce-GO-TiO2相比有了明显的红移，说明La和GO共掺杂相比Ce和GO共掺杂产生了更明显的协同效应。FIG. 1 is the ultraviolet-visible light diffuse reflectance spectrum of the photocatalyst powder prepared in Example 1 and Comparative Examples 1-3. It can be seen from Figure 1 that compared with TiO 2 , the light absorption ability of GO-TiO 2 has been significantly enhanced due to the presence of GO. However, the absorption boundary of GO-TiO 2 and TiO 2 is limited in the ultraviolet region, while the absorption threshold of La-GO-TiO 2 and Ce-GO-TiO 2 extends to the visible light range, which proves that the doping of La or Ce It can transform a catalyst that does not respond to visible light into a photocatalyst that can utilize visible light sources. The radius of La ions (106pm) is greater than that of Ce ions (103pm), so when doped with TiO 2 , La ions are more likely to cause deformation of TiO 2 crystals than Ce ions, thereby reducing the recombination rate of carriers. Compared with the Ce 4f electronic state, the La 5d electronic state is more conducive to the reduction of the band gap and the electronic transition when interacting with the Ti 3d electronic state, resulting in a red-shift in the absorption spectrum. The band gap (Eg) can be calculated by the formula, Eg=1239.8/λ, where λ(nm) is the wavelength of the spectral absorption boundary. The band gaps of single-doped GO, co-doped Ce-GO and co-doped La-GO TiO2 are 2.71, 2.41 and 2.14 eV, respectively (Table 1). Calcination of the obtained La-GO- TiO2 photocatalyst under nitrogen atmosphere can reduce the loss of GO during the calcination process. After La replaces Ce, the band gap decreases from 2.41eV to 2.14eV; combined with Figure 1, the absorption spectrum of La-GO-TiO 2 has a significant red shift compared with Ce-GO-TiO 2 , indicating that La and GO co-doping produced a more obvious synergistic effect than Ce and GO co-doping.
如图2所示，对实施例1和对比例1～3制备的光催化剂粉体进行亚甲基蓝的光催化降解实验，以一支500W的H形长弧氙灯1作为光源并安装在距离反应器高度10cm的地方，用透光膜密封反映瓶口，并在底部加磁力转子3和磁力搅拌器4搅拌，反应温度控制在5～20℃。As shown in Figure 2, the photocatalytic degradation experiment of methylene blue was carried out on the photocatalyst powders prepared in Example 1 and Comparative Examples 1-3, with a 500W H-shaped long-
结果的分析计算方法：以亚甲基蓝(MB)作为污染源，各催化剂用量为50mg，MB的浓度为10mg/L。实验开始前，先遮光搅拌60分钟，以使催化剂与MB溶液达到吸附平衡。吸附平衡后，取样留待分析得出初始浓度，再打开氙灯1开始光照试验，每隔60分钟取样一次，高速离心过滤，用分光光度计测定溶液吸光度的变化，已知MB的最大吸收波长为664nm。具体实验步骤如下：The analysis and calculation method of the result: take methylene blue (MB) as the pollution source, the dosage of each catalyst is 50 mg, and the concentration of MB is 10 mg/L. Before the start of the experiment, stir for 60 minutes in the dark to make the catalyst and MB solution reach adsorption equilibrium. After the adsorption balance, the sample is left for analysis to obtain the initial concentration, then turn on the
(1)在250mL的烧杯2中配置100mL的10mg/L的MB水溶液；(1) Configure 100 mL of 10 mg/L MB aqueous solution in a 250
(2)将准备好的催化剂粉体放入MB溶液中遮光搅拌60min，达到吸附平衡后再开始降解实验；(2) Put the prepared catalyst powder into the MB solution and stir for 60 minutes under shading, and start the degradation experiment after reaching the adsorption equilibrium;
(3)打开氙灯1辐照，反应60分钟后，取2mL溶液出来离心(转速5000r/mm，时间5min)。取上层清液，用分光光度计测定溶液吸光度变化。(3) Turn on
(4)之后每隔60分钟取液一次，重复上述步骤至实验结束。(4) After that, the liquid was taken every 60 minutes, and the above steps were repeated until the end of the experiment.
从以上试验中，可以获得MB随模拟日光辐照时间(t)而改变的变量(C/Co)，它可以反映MB浓度的减少，其中Co是亚甲基蓝的初始浓度，C为反应过程中检测到的亚甲基蓝的量。亚甲基蓝的降解效率可以作为评价催化剂活性的标准，实验结果见图3。From the above experiments, the variable (C/Co) that MB changes with the simulated sunlight irradiation time (t) can be obtained, which can reflect the reduction of MB concentration, where Co is the initial concentration of methylene blue, and C is the detected concentration of methylene blue during the reaction. amount of methylene blue. The degradation efficiency of methylene blue can be used as a standard for evaluating catalyst activity, and the experimental results are shown in Figure 3.
如图3所示，在光催化降解实验中设有空白组，在未添加光催化剂的条件下，无光照都对MB影响不大，MB都很难被降解，经过5个小时的模拟日光辐照后，MB的降解效率小于5％。对比例1制备的TiO2光催化剂对MB的降解效率约为20％；对比例2中将TiO2负载在氧化石墨烯(GO)上形成GO-TiO2复合光催化剂粉体，与单独的TiO2相比，对MB的光降解率提高了2倍还多；对比例3中制备的Ce-GO-TiO2光催化剂在氙灯照射3h、5h后对MB的降解效率分别为84.7％、98.1％。与对比例3制备的光催化剂相比，实施例1制备的La-GO-TiO2光催化剂具有更好的可见光光催化活性，在氙灯照射3h后对MB的降解效率就达到了98.5％，5h后达到了99.3％。从光催化实验的结果看，实施例1在更短的时间里超过了对比例3的效果，在氙灯辐照3h后，实施例1对MB的光催化效率相比对比例3提高了13.8％。As shown in Figure 3, there is a blank group in the photocatalytic degradation experiment. Under the condition of no photocatalyst added, no light has little effect on MB, and MB is difficult to degrade. After 5 hours of simulated sunlight radiation After irradiation, the degradation efficiency of MB was less than 5%. The TiO photocatalyst prepared in comparative example 1 has about 20% degradation efficiency to MB; in comparative example 2 , TiO is supported on graphene oxide (GO) to form GO- TiO Composite photocatalyst powder, and independent TiO Compared with 2 , the photodegradation rate of MB has increased by more than 2 times; the Ce-GO- TiO2 photocatalyst prepared in Comparative Example 3 has a degradation efficiency of 84.7% and 98.1% for MB after xenon lamp irradiation for 3h and 5h . Compared with the photocatalyst prepared in Comparative Example 3, the La-GO- TiO photocatalyst prepared in Example 1 has better visible light photocatalytic activity, and the degradation efficiency of MB reached 98.5% after 3h of xenon lamp irradiation, and 5h After reaching 99.3%. From the results of the photocatalytic experiment, Example 1 surpassed the effect of Comparative Example 3 in a shorter time, and after 3 hours of xenon lamp irradiation, the photocatalytic efficiency of Example 1 to MB increased by 13.8% compared with Comparative Example 3 .
显然，上述实施例仅仅是为清楚地说明本发明的技术方案所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。Apparently, the above-mentioned embodiments are only examples for clearly illustrating the technical solution of the present invention, rather than limiting the implementation of the present invention. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is not necessary and impossible to exhaustively list all the implementation manners here. All modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the claims of the present invention.
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