CN103464138B - Ytterbium doped bismuth vanadate visible light photocatalyst, and preparation method and application thereof - Google Patents
Ytterbium doped bismuth vanadate visible light photocatalyst, and preparation method and application thereof Download PDFInfo
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Abstract
Description
技术领域technical field
本发明属于材料科学领域，具体涉及一种镱掺杂钒酸铋可见光光催化剂及其制备方法和应用。The invention belongs to the field of material science, and in particular relates to a visible light photocatalyst doped with ytterbium bismuth vanadate and a preparation method and application thereof.
背景技术Background technique
BiVO4是一种对可见光响应的半导体光催化剂，主要有单斜白钨矿型结构、四方白钨矿型结构和四方锆石型结构这三种晶型。大量研究证明钒酸铋的光催化性能与其晶体结构密切相关。因单斜相BiVO4禁带宽度较小（2.40eV），能吸收更多的可见光而表现出较高的光催化效率，这使其成为人们研究的焦点之一，而四方相BiVO4在可见光下光催化效率很低而被忽略。但是纯相的单斜白钨矿型结构BiVO4的光生电子和空穴的分离效率较低，导致其光催化效果并不理想，因此，近年来人们采用离子掺杂、金属负载、半导体耦合等手段对其进行了改性，在一定程度上提高了单斜相BiVO4的光催化性能。张爱平等人采用水热法制得了单斜相Ln-BiVO4，Ln=Eu，Gd，Er，其光催化效率大大提高[张爱平，张进治，Ln掺杂BiVO4(Ln=Eu，Gd，Er)光催化剂的制备和活性研究，无机化学学报，25(2009)2040-2047]。BiVO 4 is a semiconductor photocatalyst that responds to visible light. It mainly has three crystal forms: monoclinic scheelite structure, tetragonal scheelite structure and tetragonal zircon structure. A large number of studies have proved that the photocatalytic performance of bismuth vanadate is closely related to its crystal structure. Because the monoclinic phase BiVO 4 has a smaller bandgap (2.40eV), it can absorb more visible light and exhibit higher photocatalytic efficiency, which makes it one of the focuses of people's research, while the tetragonal phase BiVO 4 can absorb more visible light The photocatalytic efficiency is too low to be ignored. However, the separation efficiency of photogenerated electrons and holes in pure-phase monoclinic scheelite structure BiVO 4 is low, resulting in unsatisfactory photocatalytic effect. Therefore, in recent years, people have used ion doping, metal loading, semiconductor coupling, etc. means to modify it, which improves the photocatalytic performance of monoclinic BiVO 4 to a certain extent. Zhang Aiping and others prepared monoclinic Ln-BiVO 4 by hydrothermal method, Ln=Eu, Gd, Er, and its photocatalytic efficiency was greatly improved [Zhang Aiping, Zhang Jinzhi, Ln-doped BiVO 4 (Ln=Eu, Gd, Er) Preparation and Activity Research of Photocatalyst, Journal of Inorganic Chemistry, 25(2009) 2040-2047].
发明内容Contents of the invention
本发明的目的在于提供一种镱掺杂钒酸铋可见光光催化剂及其制备方法和应用，该方法反应时间短，工艺流程简单，制得的镱掺杂钒酸铋可见光光催化剂具有良好的可见光光催化活性。The object of the present invention is to provide a visible light photocatalyst of ytterbium doped bismuth vanadate and its preparation method and application. photocatalytic activity.
为达到上述目的，本发明采用的技术方案为：In order to achieve the above object, the technical scheme adopted in the present invention is:
一种镱掺杂钒酸铋可见光光催化剂，其主要成分为BiVO4，为四方锆石型结构，且BiVO4的晶格中含有Yb3+，其中Yb元素与Bi元素的摩尔比为(4～10):100。A visible-light photocatalyst of ytterbium-doped bismuth vanadate, whose main component is BiVO 4 , which is a tetragonal zircon structure, and the crystal lattice of BiVO 4 contains Yb 3+ , wherein the molar ratio of Yb element to Bi element is (4 ~10): 100.
一种镱掺杂钒酸铋可见光光催化剂的制备方法，包括以下步骤：A preparation method of ytterbium-doped bismuth vanadate visible light photocatalyst, comprising the following steps:
步骤1：将Bi(NO3)3·5H2O溶于水中，搅拌均匀，得铋盐溶液；将NH4VO3溶于90～100℃的水中，加热搅拌均匀，得钒盐溶液；按照Bi与V的摩尔比为1:1将钒盐溶液加入到铋盐溶液中，搅拌均匀，得到混合液;Step 1: Dissolve Bi(NO 3 ) 3 ·5H 2 O in water and stir evenly to obtain a bismuth salt solution; dissolve NH 4 VO 3 in water at 90-100°C, heat and stir evenly to obtain a vanadium salt solution; The molar ratio of Bi and V is 1:1, adding the vanadium salt solution to the bismuth salt solution, stirring evenly to obtain a mixed solution;
步骤2：调节混合液的pH值为8，搅拌均匀；Step 2: adjust the pH value of the mixture to 8, and stir evenly;
步骤3:将Yb(NO3)3·6H2O加入到调节了pH值后的混合液中，搅拌均匀，得前驱液，其中Yb与Bi的摩尔比为(4～10):100；Step 3: adding Yb(NO 3 ) 3 ·6H 2 O to the mixed solution after adjusting the pH value, stirring evenly to obtain a precursor solution, wherein the molar ratio of Yb to Bi is (4-10):100;
步骤4：将前驱液放入微波水热反应釜中，再将微波水热反应釜密封后放入微波水热反应仪中，设定微波功率为300W，从室温升温至100℃，在100℃保温6min；然后从100℃升温至150℃，在150℃保温6min；再从150℃升温至180℃，在180℃保温35min后结束反应，再自然冷却至室温；Step 4: Put the precursor liquid into the microwave hydrothermal reaction kettle, then seal the microwave hydrothermal reaction kettle and put it into the microwave hydrothermal reaction instrument, set the microwave power to 300W, raise the temperature from room temperature to 100°C, and set the temperature at 100°C Keep warm for 6 minutes; then raise the temperature from 100°C to 150°C, and keep it at 150°C for 6 minutes; then raise the temperature from 150°C to 180°C, keep it at 180°C for 35 minutes, then end the reaction, and then cool down to room temperature naturally;
步骤5：将经步骤4反应生成的沉淀物取出，洗涤、干燥，得到镱掺杂钒酸铋可见光光催化剂。Step 5: taking out the precipitate formed by the reaction in step 4, washing and drying to obtain a visible light photocatalyst of ytterbium-doped bismuth vanadate.
所述的铋盐溶液中Bi(NO3)3·5H2O的浓度为0.4mol/L；钒盐溶液中NH4VO3的浓度为0.4mol/L。The concentration of Bi(NO 3 ) 3 ·5H 2 O in the bismuth salt solution is 0.4 mol/L; the concentration of NH 4 VO 3 in the vanadium salt solution is 0.4 mol/L.
所述的步骤1中将Bi(NO3)3·5H2O溶于水中搅拌均匀所需的时间为30min；将NH4VO3溶于90～100℃的水中加热搅拌均匀所需的时间为15min；将钒盐溶液滴加到铋盐溶液中搅拌均匀所需的时间为30min。 In step 1, the time required to dissolve Bi(NO 3 ) 3 ·5H 2 O in water and stir uniformly is 30 minutes; 15min; the time required to add the vanadium salt solution dropwise to the bismuth salt solution and stir evenly is 30min.
所述的步骤2中用浓度为5mol/L的NaOH溶液调节混合液的pH值。In the step 2, a NaOH solution with a concentration of 5 mol/L is used to adjust the pH value of the mixed solution.
所述的步骤2中搅拌均匀所需的时间为30min；所述步骤3中搅拌均匀所需的时间为30min。The time required for uniform stirring in the step 2 is 30 min; the time required for uniform stirring in the step 3 is 30 min.
所述的步骤4中反应釜的填充比为50%～60%。The filling ratio of the reactor in the step 4 is 50% to 60%.
所述步骤5中的洗涤是用去离子水洗涤至中性后，再用无水乙醇洗涤。The washing in step 5 is to wash with deionized water until neutral, and then wash with absolute ethanol.
所述步骤5中的干燥是在60～70℃下干燥10～12h。The drying in the step 5 is at 60-70° C. for 10-12 hours.
镱掺杂钒酸铋可见光光催化剂用于降解有机物的应用。Ytterbium-doped bismuth vanadate visible-light photocatalyst for organic degradation applications.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明提供的镱掺杂钒酸铋可见光光催化剂的制备方法，以五水硝酸铋（Bi(NO3)3·5H2O）为铋源，偏钒酸铵（NH4VO3）为钒源，制备BiVO4，再以六水硝酸镱（Yb(NO3)3·6H2O）为镱源，对BiVO4进行Yb3+掺杂。本发明将Yb3+引入BiVO4的晶格中，提高了纯BiVO4在可见光下光催化降解有机物的效率。本发明采用微波水热法一步合成镱掺杂钒酸铋可见光光催化剂，结合了微波加热与水热法的优点，其反应条件温和，反应时间短，工艺流程简单，生产效率高，操作方便，制备周期短，目标晶体的晶相结构和形貌可控。The preparation method of ytterbium-doped bismuth vanadate visible light photocatalyst provided by the present invention uses bismuth nitrate pentahydrate (Bi(NO 3 ) 3 5H 2 O) as bismuth source, ammonium metavanadate (NH 4 VO 3 ) as vanadium source, prepare BiVO 4 , and then use ytterbium nitrate hexahydrate (Yb(NO 3 ) 3 ·6H 2 O) as the ytterbium source to do Yb 3+ doping on BiVO 4 . The present invention introduces Yb 3+ into the crystal lattice of BiVO 4 to improve the efficiency of photocatalytic degradation of organic matter by pure BiVO 4 under visible light. The invention adopts microwave hydrothermal method to synthesize ytterbium-doped bismuth vanadate visible light photocatalyst in one step, combines the advantages of microwave heating and hydrothermal method, has mild reaction conditions, short reaction time, simple process flow, high production efficiency and convenient operation. The preparation cycle is short, and the crystal phase structure and morphology of the target crystal are controllable.
本发明提供的镱掺杂钒酸铋可见光光催化剂为四方锆石型结构，其主要成分为BiVO4，且BiVO4的晶格中含有Yb3+，与以往文献报道的四方相BiVO4无光催化活性的结果显著不同，本发明制备的镱掺杂钒酸铋可见光光催化剂具有良好的可见光光催化活性，其可见光下的光催化活性明显高于相同条件下制得的未掺杂单斜相BiVO4的光催化活性，能够用于降解有机物，具有良好的应用前景。The ytterbium-doped bismuth vanadate visible light photocatalyst provided by the present invention has a tetragonal zircon structure, and its main component is BiVO 4 , and the crystal lattice of BiVO 4 contains Yb 3+ , which is dark compared with the tetragonal phase BiVO 4 reported in previous literatures. The results of catalytic activity are significantly different. The ytterbium-doped bismuth vanadate visible light photocatalyst prepared by the present invention has good visible light photocatalytic activity, and its photocatalytic activity under visible light is significantly higher than that of undoped monoclinic phase prepared under the same conditions. The photocatalytic activity of BiVO 4 can be used to degrade organic matter and has a good application prospect.
附图说明Description of drawings
图1是本发明不同Yb3+掺杂量下制备的镱掺杂钒酸铋可见光光催化剂的XRD谱图，其中a为未掺杂的BiVO4的XRD图谱，b～e分别为实施例1～实施例4制备的镱掺杂钒酸铋可见光光催化剂的XRD图谱。Figure 1 is the XRD spectrum of the visible light photocatalyst of ytterbium-doped bismuth vanadate prepared under different Yb 3+ doping amounts in the present invention, wherein a is the XRD spectrum of undoped BiVO 4 , and b~e are respectively Example 1 ~The XRD spectrum of the visible light photocatalyst of ytterbium-doped bismuth vanadate prepared in Example 4.
图2是本发明不同Yb3+掺杂量下制备的镱掺杂钒酸铋可见光光催化剂在可见光下对罗丹明B的降解率曲线，其中a为未掺杂的单斜相BiVO4催化剂对罗丹明B的降解率曲线，b～e分别为实施例1～实施例4制备的镱掺杂钒酸铋可见光光催化剂对罗丹明B的降解曲线，RhB为可见光下不加光催化剂时罗丹明B的降解率曲线。Fig. 2 is the degradation rate curve of rhodamine B under visible light by the ytterbium-doped bismuth vanadate visible light photocatalyst prepared under different Yb 3+ doping amounts in the present invention, wherein a is the undoped monoclinic phase BiVO 4 catalyst pair The degradation rate curve of Rhodamine B, b～e are the degradation curves of Rhodamine B by the visible light photocatalyst of ytterbium doped bismuth vanadate prepared in Examples 1～Example 4 respectively, and RhB is Rhodamine when no photocatalyst is added under visible light The degradation rate curve of B.
具体实施方式Detailed ways
下面结合具体实施例和附图对本发明作进一步详细说明。The present invention will be described in further detail below in conjunction with specific embodiments and accompanying drawings.
实施例1：Example 1:
一种镱掺杂钒酸铋可见光光催化剂，其主要成分为BiVO4，为四方锆石型结构，且BiVO4的晶格中含有Yb3+，其中Yb元素与Bi元素的摩尔比为4:100。A visible-light photocatalyst of ytterbium-doped bismuth vanadate, whose main component is BiVO 4 , which is a tetragonal zircon structure, and the crystal lattice of BiVO 4 contains Yb 3+ , wherein the molar ratio of Yb element to Bi element is 4: 100.
一种镱掺杂钒酸铋可见光光催化剂的制备方法，包括以下步骤：A preparation method of ytterbium-doped bismuth vanadate visible light photocatalyst, comprising the following steps:
步骤1：将0.01mol Bi(NO3)3·5H2O溶于25mL去离子水中，搅拌30min，得到Bi(NO3)3·5H2O浓度为0.4mol/L的铋盐溶液；将0.01mol NH4VO3溶于25mL90℃的去离子水中，加热搅拌15min，得到NH4VO3浓度为0.4mol/L的钒盐溶液；按照Bi与V的摩尔比为1:1将钒盐溶液逐滴加入到铋盐溶液中，搅拌30min，得到混合液；Step 1: Dissolve 0.01mol Bi(NO 3 ) 3 ·5H 2 O in 25mL of deionized water and stir for 30min to obtain a Bi(NO 3 ) 3 ·5H 2 O concentration of 0.4mol/L bismuth salt solution; mol NH 4 VO 3 was dissolved in 25 mL of deionized water at 90°C, heated and stirred for 15 min to obtain a vanadium salt solution with a NH 4 VO 3 concentration of 0.4 mol/L; Added dropwise in the bismuth salt solution, stirred for 30min to obtain a mixed solution;
步骤2：用浓度为5mol/L的NaOH溶液调节混合液的pH值为8，搅拌30min；Step 2: adjust the pH value of the mixture to 8 with a NaOH solution with a concentration of 5 mol/L, and stir for 30 minutes;
步骤3:将六水硝酸镱（Yb(NO3)3·6H2O）按照Yb与Bi的摩尔比为4:100加入到调节了pH值后的混合液中，搅拌30min，得前驱液；Step 3: Add ytterbium nitrate hexahydrate (Yb(NO 3 ) 3 6H 2 O) into the mixed solution after adjusting the pH value according to the molar ratio of Yb to Bi of 4:100, and stir for 30 minutes to obtain the precursor solution;
步骤4：将前驱液放入聚四氟乙烯材质的微波水热反应釜中，微波水热反应釜的填充比为55%，将微波水热反应釜密封后放入微波水热反应仪中，选择微波消解（温控）方案，设定微波功率为300W，从室温升温至100℃，在100℃保温6min；然后从100℃升温至150℃，在150℃保温6min；再从150℃升温至180℃，在180℃保温35min后结束反应，再自然冷却至室温；Step 4: Put the precursor liquid into a microwave hydrothermal reactor made of polytetrafluoroethylene, the filling ratio of the microwave hydrothermal reactor is 55%, seal the microwave hydrothermal reactor and put it into the microwave hydrothermal reactor, Select the microwave digestion (temperature control) scheme, set the microwave power to 300W, raise the temperature from room temperature to 100°C, and keep it at 100°C for 6 minutes; then raise the temperature from 100°C to 150°C, and keep it at 150°C for 6 minutes; 180°C, heat at 180°C for 35 minutes to end the reaction, then naturally cool to room temperature;
步骤5：将经步骤4反应生成的沉淀物取出，用去离子水洗涤至中性后，再用无水乙醇洗涤3次，再在70℃下干燥10h，得到镱掺杂钒酸铋可见光光催化剂。Step 5: Take out the precipitate formed by the reaction in step 4, wash it with deionized water to neutrality, wash it with absolute ethanol three times, and then dry it at 70°C for 10 hours to obtain ytterbium-doped bismuth vanadate visible light catalyst.
实施例2：Example 2:
一种镱掺杂钒酸铋可见光光催化剂，其主要成分为BiVO4，为四方锆石型结构，且BiVO4的晶格中含有Yb3+，其中Yb元素与Bi元素的摩尔比为6:100。A visible-light photocatalyst of ytterbium-doped bismuth vanadate, whose main component is BiVO 4 , which is a tetragonal zircon structure, and the crystal lattice of BiVO 4 contains Yb 3+ , wherein the molar ratio of Yb element to Bi element is 6: 100.
一种镱掺杂钒酸铋可见光光催化剂的制备方法，包括以下步骤：A preparation method of ytterbium-doped bismuth vanadate visible light photocatalyst, comprising the following steps:
步骤1：将0.01mol Bi(NO3)3·5H2O溶于25mL去离子水中，搅拌30min，得到Bi(NO3)3·5H2O浓度为0.4mol/L的铋盐溶液；将0.01mol NH4VO3溶于25mL95℃的去离子水中，加热搅拌15min，得到NH4VO3浓度为0.4mol/L的钒盐溶液；按照Bi与V的摩尔比为1:1将钒盐溶液逐滴加入到铋盐溶液中，搅拌30min，得到混合液；Step 1: Dissolve 0.01mol Bi(NO 3 ) 3 ·5H 2 O in 25mL of deionized water and stir for 30min to obtain a Bi(NO 3 ) 3 ·5H 2 O concentration of 0.4mol/L bismuth salt solution; mol NH 4 VO 3 was dissolved in 25 mL of deionized water at 95°C, heated and stirred for 15 min to obtain a vanadium salt solution with a NH 4 VO 3 concentration of 0.4 mol/L; Added dropwise in the bismuth salt solution, stirred for 30min to obtain a mixed solution;
步骤2：用浓度为5mol/L的NaOH溶液调节混合液的pH值为8，搅拌30min；Step 2: adjust the pH value of the mixture to 8 with a NaOH solution with a concentration of 5 mol/L, and stir for 30 minutes;
步骤3:将六水硝酸镱（Yb(NO3)3·6H2O）按照Yb与Bi的摩尔比为6:100加入到调节了pH值后的混合液中，搅拌30min，得前驱液；Step 3: Add ytterbium nitrate hexahydrate (Yb(NO 3 ) 3 6H 2 O) into the mixed solution after adjusting the pH value according to the molar ratio of Yb to Bi of 6:100, and stir for 30 minutes to obtain the precursor solution;
步骤4：将前驱液放入聚四氟乙烯材质的微波水热反应釜中，微波水热反应釜的填充比为50%，将微波水热反应釜密封后放入微波水热反应仪中，选择微波消解（温控）方案，设定微波功率为300W，从室温升温至100℃，在100℃保温6min；然后从100℃升温至150℃，在150℃保温6min；再从150℃升温至180℃，在180℃保温35min后结束反应，再自然冷却至室温；Step 4: Put the precursor liquid into a microwave hydrothermal reactor made of polytetrafluoroethylene, the filling ratio of the microwave hydrothermal reactor is 50%, seal the microwave hydrothermal reactor and put it into the microwave hydrothermal reactor, Select the microwave digestion (temperature control) scheme, set the microwave power to 300W, raise the temperature from room temperature to 100°C, and keep it at 100°C for 6 minutes; then raise the temperature from 100°C to 150°C, and keep it at 150°C for 6 minutes; 180°C, heat at 180°C for 35 minutes to end the reaction, then naturally cool to room temperature;
步骤5：将经步骤4反应生成的沉淀物取出，用去离子水洗涤至中性后，再用无水乙醇洗涤3次，再在65℃下干燥12h，得到镱掺杂钒酸铋可见光光催化剂。Step 5: Take out the precipitate formed by the reaction in step 4, wash it with deionized water until it is neutral, then wash it with absolute ethanol three times, and then dry it at 65°C for 12 hours to obtain ytterbium-doped bismuth vanadate visible light catalyst.
实施例3：Example 3:
一种镱掺杂钒酸铋可见光光催化剂，其主要成分为BiVO4，为四方锆石型结构，且BiVO4的晶格中含有Yb3+，其中Yb元素与Bi元素的摩尔比为8:100。A visible-light photocatalyst of ytterbium-doped bismuth vanadate, whose main component is BiVO 4 , which is a tetragonal zircon structure, and the crystal lattice of BiVO 4 contains Yb 3+ , wherein the molar ratio of Yb element to Bi element is 8: 100.
一种镱掺杂钒酸铋可见光光催化剂的制备方法，包括以下步骤：A preparation method of ytterbium-doped bismuth vanadate visible light photocatalyst, comprising the following steps:
步骤1：将0.01mol Bi(NO3)3·5H2O溶于25mL去离子水中，搅拌30min，得到Bi(NO3)3·5H2O浓度为0.4mol/L的铋盐溶液；将0.01mol NH4VO3溶于25mL95℃的去离子水中，加热搅拌15min，得到NH4VO3浓度为0.4mol/L的钒盐溶液；按照Bi与V的摩尔比为1:1将钒盐溶液逐滴加入到铋盐溶液中，搅拌30min，得到混合液；Step 1: Dissolve 0.01mol Bi(NO 3 ) 3 ·5H 2 O in 25mL of deionized water and stir for 30min to obtain a Bi(NO 3 ) 3 ·5H 2 O concentration of 0.4mol/L bismuth salt solution; mol NH 4 VO 3 was dissolved in 25 mL of deionized water at 95°C, heated and stirred for 15 min to obtain a vanadium salt solution with a NH 4 VO 3 concentration of 0.4 mol/L; Added dropwise in the bismuth salt solution, stirred for 30min to obtain a mixed solution;
步骤2：用浓度为5mol/L的NaOH溶液调节混合液的pH值为8，搅拌30min；Step 2: adjust the pH value of the mixture to 8 with a NaOH solution with a concentration of 5 mol/L, and stir for 30 minutes;
步骤3:将六水硝酸镱（Yb(NO3)3·6H2O）按照Yb与Bi的摩尔比为8:100加入到调节了pH值后的混合液中，搅拌30min，得前驱液；Step 3: Add ytterbium nitrate hexahydrate (Yb(NO 3 ) 3 6H 2 O) into the mixed solution after adjusting the pH value according to the molar ratio of Yb to Bi of 8:100, and stir for 30 minutes to obtain the precursor solution;
步骤4：将前驱液放入聚四氟乙烯材质的微波水热反应釜中，微波水热反应釜的填充比为60%，将微波水热反应釜密封后放入微波水热反应仪中，选择微波消解（温控）方案，设定微波功率为300W，从室温升温至100℃，在100℃保温6min；然后从100℃升温至150℃，在150℃保温6min；再从150℃升温至180℃，在180℃保温35min后结束反应，再自然冷却至室温；Step 4: Put the precursor solution into a microwave hydrothermal reactor made of polytetrafluoroethylene, the filling ratio of the microwave hydrothermal reactor is 60%, seal the microwave hydrothermal reactor and put it into the microwave hydrothermal reactor, Select the microwave digestion (temperature control) scheme, set the microwave power to 300W, raise the temperature from room temperature to 100°C, and keep it at 100°C for 6 minutes; then raise the temperature from 100°C to 150°C, and keep it at 150°C for 6 minutes; 180°C, heat at 180°C for 35 minutes to end the reaction, then naturally cool to room temperature;
步骤5：将经步骤4反应生成的沉淀物取出，用去离子水洗涤至中性后，再用无水乙醇洗涤3次，再在60℃下干燥11h，得到镱掺杂钒酸铋可见光光催化剂。Step 5: Take out the precipitate formed by the reaction in step 4, wash it with deionized water until it is neutral, wash it with absolute ethanol three times, and dry it at 60°C for 11 hours to obtain ytterbium-doped bismuth vanadate visible light catalyst.
实施例4：Example 4:
一种镱掺杂钒酸铋可见光光催化剂，其主要成分为BiVO4，为四方锆石型结构，且BiVO4的晶格中含有Yb3+，其中Yb元素与Bi元素的摩尔比为10:100。A visible-light photocatalyst of ytterbium-doped bismuth vanadate, whose main component is BiVO 4 , which is a tetragonal zircon structure, and the crystal lattice of BiVO 4 contains Yb 3+ , wherein the molar ratio of Yb element to Bi element is 10: 100.
一种镱掺杂钒酸铋可见光光催化剂的制备方法，包括以下步骤：A preparation method of ytterbium-doped bismuth vanadate visible light photocatalyst, comprising the following steps:
步骤1：将0.01mol Bi(NO3)3·5H2O溶于25mL去离子水中，搅拌30min，得到Bi(NO3)3·5H2O浓度为0.4mol/L的铋盐溶液；将0.01mol NH4VO3溶于25mL100℃的去离子水中，加热搅拌15min，得到NH4VO3浓度为0.4mol/L的钒盐溶液；按照Bi与V的摩尔比为1:1将钒盐溶液逐滴加入到铋盐溶液中，搅拌30min，得到混合液；Step 1: Dissolve 0.01mol Bi(NO 3 ) 3 ·5H 2 O in 25mL of deionized water and stir for 30min to obtain a Bi(NO 3 ) 3 ·5H 2 O concentration of 0.4mol/L bismuth salt solution; mol NH 4 VO 3 was dissolved in 25 mL of deionized water at 100°C, heated and stirred for 15 min to obtain a vanadium salt solution with a NH 4 VO 3 concentration of 0.4 mol/L; Added dropwise in the bismuth salt solution, stirred for 30min to obtain a mixed solution;
步骤2：用浓度为5mol/L的NaOH溶液调节混合液的pH值为8，搅拌30min；Step 2: adjust the pH value of the mixture to 8 with a NaOH solution with a concentration of 5 mol/L, and stir for 30 minutes;
步骤3:将六水硝酸镱（Yb(NO3)3·6H2O）按照Yb与Bi的摩尔比为10:100加入到调节了pH值后的混合液中，搅拌30min，得前驱液；Step 3: Add ytterbium nitrate hexahydrate (Yb(NO 3 ) 3 6H 2 O) into the mixed solution after adjusting the pH value according to the molar ratio of Yb to Bi of 10:100, and stir for 30 minutes to obtain the precursor solution;
步骤4：将前驱液放入聚四氟乙烯材质的微波水热反应釜中，微波水热反应釜的填充比为60%，将微波水热反应釜密封后放入微波水热反应仪中，选择微波消解（温控）方案，设定微波功率为300W，从室温升温至100℃，在100℃保温6min；然后从100℃升温至150℃，在150℃保温6min；再从150℃升温至180℃，在180℃保温35min后结束反应，再自然冷却至室温；Step 4: Put the precursor solution into a microwave hydrothermal reactor made of polytetrafluoroethylene, the filling ratio of the microwave hydrothermal reactor is 60%, seal the microwave hydrothermal reactor and put it into the microwave hydrothermal reactor, Select the microwave digestion (temperature control) scheme, set the microwave power to 300W, raise the temperature from room temperature to 100°C, and keep it at 100°C for 6 minutes; then raise the temperature from 100°C to 150°C, and keep it at 150°C for 6 minutes; 180°C, heat at 180°C for 35 minutes to end the reaction, then naturally cool to room temperature;
步骤5：将经步骤4反应生成的沉淀物取出，用去离子水洗涤至中性后，再用无水乙醇洗涤3次，再在70℃下干燥10h，得到镱掺杂钒酸铋可见光光催化剂。Step 5: Take out the precipitate formed by the reaction in step 4, wash it with deionized water to neutrality, wash it with absolute ethanol three times, and then dry it at 70°C for 10 hours to obtain ytterbium-doped bismuth vanadate visible light catalyst.
图1是不同Yb3+掺杂量下制备的镱掺杂钒酸铋可见光光催化剂的XRD图谱，其中a为未掺杂的BiVO4的XRD图谱，未掺杂的BiVO4是按照本发明的制备方法，在步骤3中不掺杂Yb(NO3)3·6H2O得到的；b～e分别为按照实施例1～实施例4的方法制备出的镱掺杂钒酸铋可见光光催化剂的XRD图谱。从图1中可以看出，未掺杂的BiVO4的所有衍射峰与PDF卡片(JCPDS NO.75-2480)相一致，说明其为单斜白钨矿型结构；掺杂后的镱掺杂钒酸铋可见光光催化剂的所有衍射峰均与PDF卡片(JCPDS NO.14-0133)吻合，说明其均为四方锆石型结构，这说明Yb3+掺杂对BiVO4的晶体结构有很大影响。Fig. 1 is the XRD pattern of ytterbium-doped bismuth vanadate visible light photocatalyst prepared under different Yb 3+ doping amount, wherein a is the XRD pattern of undoped BiVO 4 , and undoped BiVO 4 is according to the present invention The preparation method is obtained without doping Yb(NO 3 ) 3 ·6H 2 O in step 3; b~e are respectively the ytterbium-doped bismuth vanadate visible light photocatalysts prepared according to the methods of Examples 1-4 The XRD pattern. It can be seen from Figure 1 that all the diffraction peaks of undoped BiVO 4 are consistent with the PDF card (JCPDS NO.75-2480), indicating that it is a monoclinic scheelite structure; the doped ytterbium doped All the diffraction peaks of bismuth vanadate visible light photocatalysts are consistent with the PDF card (JCPDS NO.14-0133), indicating that they are all tetragonal zircon structures, which shows that Yb 3+ doping has a great influence on the crystal structure of BiVO 4 Influence.
图2是不同Yb3+掺杂量下制备的镱掺杂钒酸铋可见光光催化剂降解罗丹明B的降解率-时间曲线，其中a为未掺杂的BiVO4的降解曲线，未掺杂的BiVO4是按照本发明的制备方法，在步骤3中不掺杂Yb(NO3)3·6H2O得到的；b～e分别为按照实施例1～实施例4的方法制备出的镱掺杂钒酸铋可见光光催化剂的降解曲线。图2中纵坐标的Ct/C0为某时刻罗丹明B降解后的浓度与其初始浓度的比值。从图2中可以看出，在可见光照射下，镱掺杂钒酸铋可见光光催化剂的光催化活性均明显优于未掺杂单斜相BiVO4的光催化活性，其中实施例3制备的镱掺杂钒酸铋可见光光催化剂对罗丹明B溶液的降解率最高，可见光照射120min后罗丹明B降解率可达96.7%。因此本发明制备的镱掺杂钒酸铋可见光光催化剂能够用于降解有机物。Fig. 2 is the degradation rate-time curve of ytterbium-doped bismuth vanadate visible light photocatalyst degrading rhodamine B prepared under different Yb 3+ doping amounts, where a is the degradation curve of undoped BiVO 4 , and undoped BiVO 4 is obtained according to the preparation method of the present invention without doping Yb(NO 3 ) 3 ·6H 2 O in step 3; b~e are ytterbium doped Degradation curve of bismuth heterovanadate visible light photocatalyst. C t /C 0 on the ordinate in Fig. 2 is the ratio of the degraded concentration of rhodamine B to its initial concentration at a certain moment. It can be seen from Figure 2 that under visible light irradiation, the photocatalytic activity of ytterbium-doped bismuth vanadate visible light photocatalysts is significantly better than that of undoped monoclinic BiVO 4 , and the ytterbium prepared in Example 3 The visible light photocatalyst doped with bismuth vanadate has the highest degradation rate of rhodamine B solution, and the degradation rate of rhodamine B can reach 96.7% after visible light irradiation for 120 min. Therefore, the ytterbium-doped bismuth vanadate visible light photocatalyst prepared by the present invention can be used to degrade organic matter.
以上所述仅为本发明的一种实施方式，不是全部或唯一的实施方式，本领域普通技术人员通过阅读本发明说明书而对本发明技术方案采取的任何等效的变换，均为本发明的权利要求所涵盖。The above is only one embodiment of the present invention, not all or the only embodiment. Any equivalent transformation of the technical solution of the present invention adopted by those of ordinary skill in the art by reading the description of the present invention is the right of the present invention. covered by the requirements.
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