CN111389421B - Preparation method and application of two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material - Google Patents
Preparation method and application of two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material Download PDFInfo
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 53
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- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 16
- 229940073609 bismuth oxychloride Drugs 0.000 title claims abstract description 15
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 6
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及光催化技术领域，具体涉及一种二维层状氯氧铋和钛铌酸盐复合光催化材料的制备方法与应用。The invention relates to the technical field of photocatalysis, in particular to a preparation method and application of a two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material.
背景技术Background technique
随着我国工业的快速发展，工业废水的排放量逐年增加，引起环境的严重污染。目前，传统的有机污染废水处理方法有物理吸附法、化学沉淀方法和生物化学方法等，但是都存在一定的二次污染，处理效率低下，所需成本高等问题，不能满足可持续发展要求，而光催化降解技术应用于环境控制领域具有高效、绿色、经济、有效利用太阳能等优点。With the rapid development of my country's industry, the discharge of industrial wastewater has increased year by year, causing serious environmental pollution. At present, the traditional organic pollution wastewater treatment methods include physical adsorption method, chemical precipitation method and biochemical method, etc., but there are certain secondary pollution, low treatment efficiency, high cost and other problems, which cannot meet the requirements of sustainable development. The application of photocatalytic degradation technology in the field of environmental control has the advantages of high efficiency, greenness, economy, and effective use of solar energy.
目前，光催化材料面临着合成工艺复杂、可见光利用率低、催化效率低和高能耗等问题，这使得其在工业生产及实际应用中受到了限制。At present, photocatalytic materials are facing problems such as complex synthesis process, low utilization rate of visible light, low catalytic efficiency and high energy consumption, which limit their industrial production and practical application.
发明内容Contents of the invention
针对现有技术的不足，本发明的目的在于提供一种二维层状氯氧铋和钛铌酸盐复合光催化材料的制备方法与应用，本发明通过结合使用高温固相法、质子交换法、剥离-重组法和水热法制备出具有较高活性的可见光响应的BHT光催化复合材料，所述复合光催化剂为层状复合材料异质结的构筑，具有较强的可见光催化降解活性，另外该方法制备工艺简单，能耗低，所制的氮掺杂复合材料催化效率高，这些都有利于其在光催化领域的实际应用。In view of the deficiencies in the prior art, the purpose of the present invention is to provide a preparation method and application of a two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material. , exfoliation-recombination method and hydrothermal method to prepare a BHT photocatalytic composite material with high activity visible light response. In addition, the method has simple preparation process, low energy consumption, and the prepared nitrogen-doped composite material has high catalytic efficiency, all of which are beneficial to its practical application in the field of photocatalysis.
为解决现有技术问题，本发明采取的技术方案为：In order to solve the problems of the prior art, the technical scheme that the present invention takes is:
一种二维层状氯氧铋和钛铌酸盐复合光催化材料的制备方法，包括以下步骤：A preparation method of a two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material, comprising the following steps:
步骤1，按照摩尔比为1.1:1:4称取原料Cs2CO3、Nb2O5、TiO2，混合后置于研钵中充分研磨，再将粉碎后的粉末置于马弗炉中，在750-1050℃高温煅烧，合成前驱体CsTi2NbO7；
步骤2，将前驱体CsTi2NbO7与1～2mol/L的HNO3溶液进行反应，所得样品进行洗涤和干燥处理，得到HTi2NbO7；
步骤3，将HTi2NbO7分散在去离子水中得悬浮液，并向悬浮液中添加四丁基氢氧化铵溶液进行剥离，直至pH值达到9.5～10.0，室温下搅拌7天后，离心取上层清液，即得HTi2NbO7纳米片溶胶；
步骤4，将形成的HTi2NbO7纳米片溶胶中，加入0.1mM～0.5mM的低浓度HNO3溶液进行沉降即为H+重组的HTi2NbO7纳米片溶胶；
步骤5，取60-80mL H+重组的HTi2NbO7纳米片溶胶，进行磁力搅拌0.5小时保证HTN分散均匀，然后将0.4mmol的KCl和0.4mmol Bi(NO3)3·5H2O、0.2mmol的KCl和0.4mmol Bi(NO3)3·5H2O、0.6mmol的KCl和0.4mmol Bi(NO3)3·5H2O、0.8mmol的KCl和0.4mmol Bi(NO3)3·5H2O逐滴加入到上述溶液中并进行磁力搅拌1小时，将均匀的悬浮液转移到不锈钢外套聚四氟乙烯内胆的高压水热反应釜中，在160℃下反应24小时，通过高速离心，获得沉淀产物，即二维BiOCl/HTN纳米片的复合异质结；
步骤6，将获得的二维BiOCl/HTN纳米片的复合异质结进行洗涤干燥，即得BiOCl/HTN纳米片复合材料(BHT)。In step 6, the obtained composite heterojunction of two-dimensional BiOCl/HTN nanosheets is washed and dried to obtain a BiOCl/HTN nanosheet composite material (BHT).
作为改进的是，步骤1中所用的原料Cs2CO3、Nb2O5、TiO2均为分析纯，高温煅烧的升温速度保持在5～10℃/min，且在煅烧过程中分别在750℃,950℃,1050℃上各保温12小时。As an improvement, the raw materials Cs 2 CO 3 , Nb 2 O 5 , and TiO 2 used in
作为改进的是，步骤2中将5g CsTi2NbO7加入到500mL浓度为1mol/L HNO3溶液中，60℃不停搅拌处理72小时，每隔24小时换一次HNO3溶液。As an improvement, in
作为改进的是，步骤3中离心的速率为3000r/min。As an improvement, the speed of centrifugation in
作为改进的是，步骤4中低浓度HNO3溶液为0.1mol/L。As an improvement, the low-concentration HNO solution in
作为改进的是，步骤3中离心取上层剥离纳米片溶胶，离心速率为3000r/min.As an improvement, in
作为改进的是，步骤4中使用的低浓度HNO3溶液沉降，HNO3浓度为0.1mol/L。As an improvement, the low-concentration HNO3 solution used in
作为改进的是，步骤6中洗涤干燥的具体步骤：用体积比为1:1的无水乙醇水溶液冲洗二维BiOCl/HTN纳米片的复合异质结5～10次后，置于60℃的真空环境下干燥，洗涤去除BHT表面残留杂质。As an improvement, the specific steps of washing and drying in step 6: rinse the composite heterojunction of two-dimensional BiOCl/HTN nanosheets with an aqueous solution of absolute ethanol with a volume ratio of 1:1 for 5 to 10 times, and then place it in a 60°C Dry under vacuum environment, wash to remove residual impurities on the surface of BHT.
上述方法制备的二维层状氯氧铋和钛铌酸盐复合光催化材料在降解RhB溶液上的应用。The application of the two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material prepared by the above method in the degradation of RhB solution.
工作原理：一方面，BiOCl纳米片本身特殊的能带结构，具备一定的可见光响应能力；另一方面，材料复合后形成的层-层异质结结构，这种面-面接触结构，可以有利于的光生电子-空穴对的快速分离，从而提高量子产率，因此在可见光响应范围内，也提高光催化降解性能。Working principle: On the one hand, the special energy band structure of BiOCl nanosheets has a certain visible light response ability; on the other hand, the layer-layer heterojunction structure formed after material compounding, this surface-surface contact structure, can It is beneficial to the rapid separation of photogenerated electron-hole pairs, thereby improving the quantum yield, and therefore also improving the photocatalytic degradation performance in the visible light response range.
有益效果：Beneficial effect:
与现有技术相比，本发明一种二维层状氯氧铋和钛铌酸盐复合光催化材料的制备方法得到优势在于：首先采用高温固相法制备层状CsTi2NbO7作为前驱体，通过与硝酸进行质子交换四丁基氢氧化铵(TBAOH)溶液进行柱撑剥离反应，得到HTi2NbO7纳米片悬浮液，用稀硝酸沉降获得氢离子重组的纳米片溶胶HTN。以KCl和Bi(NO3)3·5H2O作为BiOCl纳米片的反应前驱体，将一定量的KCl和Bi(NO3)3·5H2O加入HTN搅拌均匀后进行水热处理，从而成功合成了新型2D/2D BiOCl/HTN纳米片(BHT)复合材料。该制备方法工艺简单，设备要求低，成本低，所制备的层状复合材料光催化效率高，对RhB具有优异的降解效果。Compared with the prior art, the preparation method of a two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material of the present invention has the advantages that: firstly, the layered CsTi 2 NbO 7 is prepared as a precursor by a high-temperature solid-state method , by exchanging tetrabutylammonium hydroxide (TBAOH) solution with nitric acid for pillar exfoliation reaction, HTi 2 NbO 7 nanosheet suspension was obtained, and hydrogen ion recombined nanosheet sol HTN was obtained by precipitation with dilute nitric acid. Using KCl and Bi(NO 3 ) 3 ·5H 2 O as the reaction precursors of BiOCl nanosheets, a certain amount of KCl and Bi(NO 3 ) 3 ·5H 2 O was added to HTN and stirred evenly, followed by hydrothermal treatment to successfully synthesize A novel 2D/2D BiOCl/HTN nanosheet (BHT) composite material. The preparation method has simple process, low equipment requirements and low cost, and the prepared layered composite material has high photocatalytic efficiency and excellent degradation effect on RhB.
附图说明Description of drawings
图1为本发明实施例1中每步制备的样品CsTi2NbO7，HTi2NbO7，HTN，BHT的XRD图，其中BiOCl为对比例1制备样品；Fig. 1 is the sample CsTi2NbO7 prepared in each step in the embodiment of the
图2为本发明实施例1中所制样品，以及对比例1制备的样品BiOCl的电镜图：(a)HTN纳米片的FEEM图,(b)BiOCl的FESEM图，(c)BHT的FESEM图，(d)、(e)和(f)均为BHT的HRTEM图；Fig. 2 is the electron micrograph of the sample prepared in Example 1 of the present invention, and the sample BiOCl prepared in Comparative Example 1: (a) FEEM figure of HTN nanosheet, (b) FESEM figure of BiOCl, (c) FESEM figure of BHT , (d), (e) and (f) are HRTEM images of BHT;
图3为本发明实施例1中样品HTN和BHT的可见光催化RhB溶液降解图，其中BiOCl为对比例1制备样品；Fig. 3 is the visible light-catalyzed RhB solution degradation diagram of samples HTN and BHT in Example 1 of the present invention, wherein BiOCl is the sample prepared in Comparative Example 1;
图4为本发明实施例1中BHT复合材料可见光催化降解RhB溶液的不同时间对应的紫外-可见光分光光谱曲线图；Fig. 4 is the ultraviolet-visible light spectroscopic curve graph corresponding to different times of BHT composite material visible light catalytic degradation RhB solution in Example 1 of the present invention;
图5为本发明实施例1中层状BHT复合材料经过5次循环后，可见光催化降解RhB溶液效果图；Fig. 5 is the effect diagram of visible light catalytic degradation of RhB solution after 5 cycles of the layered BHT composite material in Example 1 of the present invention;
图6为本发明冷凝装置实物图。Fig. 6 is a physical diagram of the condensing device of the present invention.
具体实例方式Concrete example method
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.
实施例1Example 1
(1)通过高温固相法合成CsTi2NbO7，即采用原料为分析纯的Cs2CO3、Nb2O5、TiO2，按照1.1:1:4摩尔比混合，置于研钵中充分研磨，将混合研磨后的样品置于马弗炉，分别在750,950,1050℃各保温12小时，升温速度为10℃/min，合成前驱体CsTi2NbO7。(1) Synthesize CsTi2NbO7 by high-temperature solid-phase method, that is, use raw materials as analytically pure Cs2CO3, Nb2O5, and TiO2, mix them according to the molar ratio of 1.1:1:4, place them in a mortar and grind them thoroughly, and place the mixed and ground samples in The muffle furnace was kept at 750, 950, and 1050°C for 12 hours respectively, and the heating rate was 10°C/min to synthesize the precursor CsTi 2 NbO 7 .
(2)采用离子交换法制备HTi2NbO7：将5.0g的CsTi2NbO7加入到500mL的HNO3(1mol/L)溶液中，在不断搅拌下60℃处理72小时，每隔24小时换一次相同体积浓度的HNO3，将样品洗涤至中性干燥处理。(2) Preparation of HTi 2 NbO 7 by ion exchange method: Add 5.0g of CsTi 2 NbO 7 into 500mL of HNO 3 (1mol/L) solution, treat at 60°C for 72 hours under constant stirring, and change the temperature every 24 hours Once with HNO 3 of the same volume concentration, the sample was washed to neutral dryness.
(3)将3.0g层状HTi2NbO7分散在300mL去离子水中，再将一定量的四丁基氢氧化铵溶液(TBAOH)逐滴加入到上述悬浮液中，直至pH值达到9.5～10.0之间，在室温下搅拌7天。将所得的溶液在高速离心机中离心分离，取上层清液，即为HTi2NbO7纳米片溶胶，称量残余粉末干燥后的质量，确定HTi2NbO7纳米片溶胶的浓度，将体积浓度确定的HTi2NbO7纳米片溶胶继续搅拌均匀，逐滴加入一定量的0.1mol/L的HNO3溶液进行沉降，获得H+重组后的HTN。(3) Disperse 3.0g of layered HTi2NbO7 in 300mL of deionized water , and then add a certain amount of tetrabutylammonium hydroxide solution (TBAOH) dropwise to the above suspension until the pH value reaches between 9.5 and 10.0 , stirred at room temperature for 7 days. Centrifuge the resulting solution in a high-speed centrifuge, take the supernatant, which is the HTi 2 NbO 7 nanosheet sol, weigh the quality of the residual powder after drying, determine the concentration of the HTi 2 NbO 7 nanosheet sol, and divide the volume concentration The determined HTi 2 NbO 7 nanosheet sol was continuously stirred evenly, and a certain amount of 0.1 mol/L HNO 3 solution was added dropwise for precipitation to obtain H + recombined HTN.
(4)取60mL的HTN进行磁力搅拌0.5小时，确保HTN纳米片重新分散均匀；然后将0.4mmol的KCl和0.4mmol的Bi(NO3)3·5H2O逐滴加入到上述溶液中并进行磁力搅拌1小时，所得的溶液转移到水热反应釜，160℃下反应24小时；最后将上述所得样品用去离子水和无水乙醇的混合溶液洗数次，并在60℃下干燥即可获得层状BiOCl/HTN复合材料(缩写为BHT)。(4) Take 60mL of HTN and carry out magnetic stirring for 0.5 hours to ensure that the HTN nanosheets are redispersed evenly; Magnetically stirred for 1 hour, the obtained solution was transferred to a hydrothermal reaction kettle, and reacted at 160°C for 24 hours; finally, the above obtained sample was washed several times with a mixed solution of deionized water and absolute ethanol, and dried at 60°C A layered BiOCl/HTN composite (abbreviated as BHT) was obtained.
实施例2Example 2
(1)通过高温固相法合成CsTi2NbO7，即采用原料为分析纯的Cs2CO3、Nb2O5、TiO2，按照1.1:1:4摩尔比混合，置于研钵中充分研磨，将混合研磨后的样品置于马弗炉，分别在750,950,1050℃各保温12小时，升温速度为10℃/min，合成前驱体CsTi2NbO7。(1) Synthesize CsTi 2 NbO 7 by high-temperature solid-phase method, that is, use analytically pure Cs 2 CO 3 , Nb 2 O 5 , and TiO 2 as raw materials, mix them according to the molar ratio of 1.1:1:4, and place them in a mortar to fully Grinding, the mixed and ground samples were placed in a muffle furnace and kept at 750, 950, and 1050°C for 12 hours respectively, and the heating rate was 10°C/min to synthesize the precursor CsTi 2 NbO 7 .
(2)采用离子交换法制备HTi2NbO7：将5.0g的CsTi2NbO7加入到500mL的HNO3(1mol/L)溶液中，在不断搅拌下60℃处理72小时，每隔24小时换一次相同体积浓度的HNO3，将样品洗涤至中性干燥处理。(2) Preparation of HTi 2 NbO 7 by ion exchange method: Add 5.0g of CsTi 2 NbO 7 into 500mL of HNO 3 (1mol/L) solution, treat at 60°C for 72 hours under constant stirring, and change the temperature every 24 hours Once with HNO 3 of the same volume concentration, the sample was washed to neutral dryness.
(3)将3.0g层状HTi2NbO7分散在300mL去离子水中，再将一定量的四丁基氢氧化铵溶液(TBAOH)逐滴加入到上述悬浮液中，直至pH值达到9.5～10.0之间，在室温下搅拌7天。将所得的溶液在高速离心机中离心分离，取上层清液，即为HTi2NbO7纳米片溶胶，称量残余粉末干燥后的质量，确定HTi2NbO7纳米片溶胶的浓度，将体积浓度确定的HTi2NbO7纳米片溶胶继续搅拌均匀，逐滴加入一定量的0.1mol/L的HNO3溶液进行沉降，获得H+重组后的HTN。(3) Disperse 3.0g of layered HTi2NbO7 in 300mL of deionized water , and then add a certain amount of tetrabutylammonium hydroxide solution (TBAOH) dropwise to the above suspension until the pH value reaches between 9.5 and 10.0 , stirred at room temperature for 7 days. Centrifuge the resulting solution in a high-speed centrifuge, take the supernatant, which is the HTi 2 NbO 7 nanosheet sol, weigh the quality of the residual powder after drying, determine the concentration of the HTi 2 NbO 7 nanosheet sol, and divide the volume concentration The determined HTi 2 NbO 7 nanosheet sol was continuously stirred evenly, and a certain amount of 0.1 mol/L HNO 3 solution was added dropwise for precipitation to obtain H + recombined HTN.
(4)取60mL的HTN进行磁力搅拌0.5小时，确保HTN纳米片重新分散均匀；然后将0.2mmol的KCl和0.4mmol的逐滴加入到上述溶液中并进行磁力搅拌1小时，所得的溶液转移到水热反应釜，160℃下反应24小时；最后将上述所得样品用去离子水和无水乙醇的混合溶液洗数次，并在60℃下干燥即可获得层状BiOCl/HTN复合材料(缩写为BHT)。(4) Get 60mL of HTN and carry out magnetic stirring for 0.5 hours to ensure that the HTN nanosheets are redispersed evenly; Hydrothermal reaction kettle, react at 160°C for 24 hours; finally wash the above-mentioned samples with a mixed solution of deionized water and absolute ethanol several times, and dry at 60°C to obtain a layered BiOCl/HTN composite material (abbreviation for BHT).
实施例3Example 3
(1)通过高温固相法合成CsTi2NbO7，即采用原料为分析纯的Cs2CO3、Nb2O5、TiO2，按照1.1:1:4摩尔比混合，置于研钵中充分研磨，将混合研磨后的样品置于马弗炉，分别在750，950，1050℃各保温12小时，升温速度为10℃/min，合成前驱体CsTi2NbO7。(1) Synthesize CsTi 2 NbO 7 by high-temperature solid-phase method, that is, use analytically pure Cs 2 CO 3 , Nb 2 O 5 , and TiO 2 as raw materials, mix them according to the molar ratio of 1.1:1:4, and place them in a mortar to fully Grinding, the mixed and ground samples were placed in a muffle furnace, and kept at 750, 950, and 1050°C for 12 hours respectively, with a heating rate of 10°C/min, to synthesize the precursor CsTi 2 NbO 7 .
(2)采用离子交换法制备HTi2NbO7：将5.0g的CsTi2NbO7加入到500mL的HNO3(1mol/L)溶液中，在不断搅拌下60℃处理72小时，每隔24小时换一次相同体积浓度的HNO3，将样品洗涤至中性干燥处理。(2) Preparation of HTi 2 NbO 7 by ion exchange method: Add 5.0g of CsTi 2 NbO 7 into 500mL of HNO 3 (1mol/L) solution, treat at 60°C for 72 hours under constant stirring, and change the temperature every 24 hours Once with HNO 3 of the same volume concentration, the sample was washed to neutral dryness.
(3)将3.0g层状HTi2NbO7分散在300mL去离子水中，再将一定量的四丁基氢氧化铵溶液(TBAOH)逐滴加入到上述悬浮液中，直至pH值达到9.5～10.0之间，在室温下搅拌7天。将所得的溶液在高速离心机中离心分离，取上层清液，即为HTi2NbO7纳米片溶胶，称量残余粉末干燥后的质量，确定HTi2NbO7纳米片溶胶的浓度，将体积浓度确定的HTi2NbO7纳米片溶胶继续搅拌均匀，逐滴加入一定量的0.1mol/L的HNO3溶液进行沉降，获得H+重组后的HTN。(3) Disperse 3.0g of layered HTi2NbO7 in 300mL of deionized water , and then add a certain amount of tetrabutylammonium hydroxide solution (TBAOH) dropwise to the above suspension until the pH value reaches between 9.5 and 10.0 , stirred at room temperature for 7 days. Centrifuge the resulting solution in a high-speed centrifuge, take the supernatant, which is the HTi 2 NbO 7 nanosheet sol, weigh the quality of the residual powder after drying, determine the concentration of the HTi 2 NbO 7 nanosheet sol, and divide the volume concentration The determined HTi 2 NbO 7 nanosheet sol was continuously stirred evenly, and a certain amount of 0.1 mol/L HNO 3 solution was added dropwise for precipitation to obtain H + recombined HTN.
(4)取60mL的HTN进行磁力搅拌0.5小时，确保HTN纳米片重新分散均匀；然后将0.6mmol的KCl和0.4mmol的逐滴加入到上述溶液中并进行磁力搅拌1小时，所得的溶液转移到水热反应釜，160℃下反应24小时；最后将上述所得样品用去离子水和无水乙醇的混合溶液洗数次，并在60℃下干燥即可获得层状BiOCl/HTN复合材料(缩写为BHT)。(4) Get 60mL of HTN and carry out magnetic stirring for 0.5 hours to ensure that the HTN nanosheets are redispersed evenly; Hydrothermal reaction kettle, react at 160°C for 24 hours; finally wash the above-mentioned samples with a mixed solution of deionized water and absolute ethanol several times, and dry at 60°C to obtain a layered BiOCl/HTN composite material (abbreviation for BHT).
实施例4Example 4
(1)通过高温固相法合成CsTi2NbO7，即采用原料为分析纯的Cs2CO3、Nb2O5、TiO2，按照1.1:1:4摩尔比混合，置于研钵中充分研磨，将混合研磨后的样品置于马弗炉，分别在750,950,1050℃各保温12小时，升温速度为10℃/min，合成前驱体CsTi2NbO7。(1) Synthesize CsTi 2 NbO 7 by high-temperature solid-phase method, that is, use analytically pure Cs 2 CO 3 , Nb 2 O 5 , and TiO 2 as raw materials, mix them according to the molar ratio of 1.1:1:4, and place them in a mortar to fully Grinding, the mixed and ground samples were placed in a muffle furnace and kept at 750, 950, and 1050°C for 12 hours respectively, and the heating rate was 10°C/min to synthesize the precursor CsTi 2 NbO 7 .
(2)采用离子交换法制备HTi2NbO7：将5.0g的CsTi2NbO7加入到500mL的HNO3(1mol/L)溶液中，在不断搅拌下60℃处理72小时，每隔24小时换一次相同体积浓度的HNO3，将样品洗涤至中性干燥处理。(2) Preparation of HTi 2 NbO 7 by ion exchange method: Add 5.0g of CsTi 2 NbO 7 into 500mL of HNO 3 (1mol/L) solution, treat at 60°C for 72 hours under constant stirring, and change the temperature every 24 hours Once with HNO 3 of the same volume concentration, the sample was washed to neutral dryness.
(3)将3.0g层状HTi2NbO7分散在300mL去离子水中，再将一定量的四丁基氢氧化铵溶液(TBAOH)逐滴加入到上述悬浮液中，直至pH值达到9.5～10.0之间，在室温下搅拌7天。将所得的溶液在高速离心机中离心分离，取上层清液，即为HTi2NbO7纳米片溶胶，称量残余粉末干燥后的质量，确定HTi2NbO7纳米片溶胶的浓度，将体积浓度确定的HTi2NbO7纳米片溶胶继续搅拌均匀，逐滴加入一定量的0.1mol/L的HNO3溶液进行沉降，获得H+重组后的HTN。(3) Disperse 3.0g of layered HTi2NbO7 in 300mL of deionized water , and then add a certain amount of tetrabutylammonium hydroxide solution (TBAOH) dropwise to the above suspension until the pH value reaches between 9.5 and 10.0 , stirred at room temperature for 7 days. Centrifuge the resulting solution in a high-speed centrifuge, take the supernatant, which is the HTi 2 NbO 7 nanosheet sol, weigh the quality of the residual powder after drying, determine the concentration of the HTi 2 NbO 7 nanosheet sol, and divide the volume concentration The determined HTi 2 NbO 7 nanosheet sol was continuously stirred evenly, and a certain amount of 0.1 mol/L HNO 3 solution was added dropwise for precipitation to obtain H + recombined HTN.
(4)取60mL的HTN进行磁力搅拌0.5小时，确保HTN纳米片重新分散均匀；然后将0.8mmol的KCl和0.4mmol的逐滴加入到上述溶液中并进行磁力搅拌1小时，所得的溶液转移到水热反应釜，160℃下反应24小时；最后将上述所得样品用去离子水和无水乙醇的混合溶液洗数次，并在60℃下干燥即可获得层状BiOCl/HTN复合材料(缩写为BHT)。(4) Get 60mL of HTN and carry out magnetic stirring for 0.5 hours to ensure that the HTN nanosheets are redispersed evenly; Hydrothermal reaction kettle, react at 160°C for 24 hours; finally wash the above-mentioned samples with a mixed solution of deionized water and absolute ethanol several times, and dry at 60°C to obtain a layered BiOCl/HTN composite material (abbreviation for BHT).
对比例 单一BiOCl的制备The preparation of comparative example single BiOCl
将8mL的钛酸异丙酯缓慢逐滴加入到60mL蒸馏水中磁力搅拌1小时，搅拌均匀，将所得的溶液转移到水热反应釜中，160℃下反应24小时；最后将上述所得样品用去离子水和无水乙醇的混合溶液洗数次，并在60℃下干燥，获得单一BiOCl。Slowly add 8 mL of isopropyl titanate dropwise into 60 mL of distilled water with magnetic stirring for 1 hour, stir evenly, transfer the resulting solution to a hydrothermal reaction kettle, and react at 160°C for 24 hours; The mixed solution of ionized water and absolute ethanol was washed several times and dried at 60 °C to obtain a single BiOCl.
性能测试Performance Testing
为了对本发明实施例中得到的二维层状复合光催化剂的自身品质和催化性能进行验证和分析，本试验例对实施例1～4所得的BiOCl/HTN复合光催化剂，以及单一BiOCl进行了试验，测试分析结果表现均较好，具体地，以实施例1作为实验例进行说明：In order to verify and analyze the self-quality and catalytic performance of the two-dimensional layered composite photocatalyst obtained in the examples of the present invention, this test example tested the BiOCl/HTN composite photocatalyst obtained in Examples 1 to 4, and a single BiOCl , the test and analysis results are all good, specifically, take Example 1 as an experimental example for illustration:
首先，本试验例对所测样品进行了鉴定，分别对CsTi2NbO7，HTN和层状复合BiOCl/HTN纳米片(BHT)进行X射线粉末衍射分析测试，其结果如图1所示，根据索引对照CsTi2NbO7样品的XRD图谱与标准卡片(PDF：73-0680)一致。所制备的CsTi2NbO7即是显示为层棒状结构特征。而酸化剥离柱撑H+重组后的HTN，与原始层棒状CsTi2NbO7相比，所有特征峰均消失，只有主晶面(020)特征衍射峰向小角度偏转，说明结晶度降低，原始层状结构的消失，并且剥离纳米片的堆砌使得(020)像小角度偏移。为了做比较，单纯BiOCl也被成功制备，XRD结果与标准卡片(PDF：82-0485)一致。BHT与BiOCl具有相似的XRD衍射峰，2θ＝10°，24°和26°处的几个主要(001)，(002)和(101)较强特征衍射峰，说明层状复合物中BiOCl的形成，但是，发现一些HTN的层状特征衍射峰，比如(020)这种层状结构衍射峰消失，经分析很可能水热过程中层状复合物的形成，BiOCl的较强衍射峰覆盖了HTN的特征衍射峰。综合上述，BiOCl纳米片产生并且均匀的分布在HTN纳米片上，形成一种面面接触的二维层状异质结结构。First of all, in this test example, the tested samples were identified, and X-ray powder diffraction analysis was carried out on CsTi 2 NbO 7 , HTN and layered composite BiOCl/HTN nanosheets (BHT). The results are shown in Figure 1. According to The XRD pattern of the index control CsTi 2 NbO 7 sample is consistent with the standard card (PDF: 73-0680). The as-prepared CsTi 2 NbO 7 is characterized by a layered rod-like structure. Compared with the rod-like CsTi 2 NbO 7 in the original layer, all the characteristic peaks of HTN after the acidification exfoliated the pillared H + recombination disappeared, and only the characteristic diffraction peak of the main crystal plane (020) was deflected to a small angle, indicating that the crystallinity decreased and the original The disappearance of the layered structure and the stacking of exfoliated nanosheets make the (020) image shifted at a small angle. For comparison, pure BiOCl was also successfully prepared, and the XRD results were consistent with the standard card (PDF: 82-0485). BHT and BiOCl have similar XRD diffraction peaks, several main (001), (002) and (101) strong characteristic diffraction peaks at 2θ = 10°, 24° and 26°, indicating that BiOCl in the layered composite However, it was found that some layered characteristic diffraction peaks of HTN, such as (020) layered structure diffraction peaks disappeared, after analysis, it is likely that the formation of layered complexes in the hydrothermal process, the stronger diffraction peaks of BiOCl covered The characteristic diffraction peaks of HTN. In summary, the BiOCl nanosheets are produced and uniformly distributed on the HTN nanosheets, forming a two-dimensional layered heterojunction structure with surface-to-surface contact.
为了进一步证明上述关于物质鉴定的部分推测和进一步地分析研究HTN，BiOCl和BHT光催化材料的微观形貌特征，本试验例对其进行了扫描电镜，透射电镜测试(TEM)和高分辨率透射电镜测试(HRTEM)，测试结果如图2所示。参照图2(a)可以看出，HTN近似于单层薄膜状层层堆砌，可以认为前驱体钛铌酸盐已成功剥离成纳米片。如图2(b)所示，单一的BiOCl纳米片呈小圆薄片状，尺寸大小均匀，紧密堆砌，材料表面凹凸不平，可能是纳米片不规则堆砌形成的。进一步对复合物BHT形貌观察，如图2(c)，原始HTN形状规则的层状纳米片和单纯圆片状BiOCl纳米片的结构均消失，复合物呈现出尺寸均匀，不规则排布的片状结构，并且表面存在较多形成的孔洞；为了进一步验证层状复合物的成功制备，图2(e)直观表明，两组纳米片结构的成功复合形成的一种异质结结构，通过图2(d)晶格参数表征，晶面间距d＝0.282nm，即是BiOCl纳米片暴露晶面(004)，图2(f)的晶格参数d＝0.182nm则是HTN(002)暴露晶面。证实复合物中两组组分存在，也证明了复合物的成功合成。In order to further prove the above-mentioned part of speculation about substance identification and further analyze and study the microscopic morphology characteristics of HTN, BiOCl and BHT photocatalytic materials, this test example carried out scanning electron microscopy, transmission electron microscopy (TEM) and high-resolution transmission Electron microscope test (HRTEM), the test results are shown in Figure 2. Referring to Figure 2(a), it can be seen that HTN is similar to a single-layer film-like layer stacking, and it can be considered that the precursor titanium niobate has been successfully exfoliated into nanosheets. As shown in Figure 2(b), a single BiOCl nanosheet is in the shape of a small round sheet, uniform in size, tightly packed, and the surface of the material is uneven, which may be formed by the irregular stacking of nanosheets. Further observing the morphology of the composite BHT, as shown in Figure 2(c), the structure of the regular shape of the original HTN layered nanosheets and the simple disc-shaped BiOCl nanosheets disappeared, and the composite showed a uniform size and irregular arrangement. Sheet-like structure, and there are many holes formed on the surface; in order to further verify the successful preparation of the layered composite, Figure 2(e) intuitively shows that a heterojunction structure formed by the successful composite of two sets of nanosheet structures, through Figure 2(d) lattice parameter characterization, the interplanar distance d=0.282nm, that is, the exposed crystal plane (004) of BiOCl nanosheets, and the lattice parameter d=0.182nm in Figure 2(f) is HTN(002) exposed Planes. The existence of two groups of components in the complex was confirmed, which also proved the successful synthesis of the complex.
进一步地，为了验证BHT可见光催化剂的降解能力，本试验还对实施例1中所制备的样品进行全面了可见光催化降解RhB实验，采用300W的氙灯作为模拟光源，前置一个滤波片过滤掉波长短于420nm的紫外光保留可见光光谱，以浓度为10mg/L的RhB溶液模拟含有有机污染物的污水水体，主要对所制备的HTN，BiOCl和BHT进行降解效果的对比，光催化剂的添加含量均为100mg，在光照之前，进行暗吸附反应，以达到催化剂跟目标分子充分接触，吸附饱和状态，在光照开始后，光催化反应在市售双层烧杯作为冷凝装置(如图6所示)中进行，目的去除光照过程中热效应对催化性能的影响,间隔15min取一组样品，通过液体紫外测试目标溶液RhB溶液的浓度变化表征催化剂的光催化性能。从图3中可以看出其中复合物的催化效果明显优于单一组分。采用紫外-可见光分光光谱测试RhB溶液定时定量的浓度变化，图4中可以看出复合物BHT在可见光下催化降解RhB溶液，RhB溶液浓度随光催化时间的增加，浓度的逐渐降低。Further, in order to verify the degradation ability of the BHT visible light catalyst, this experiment also carried out a comprehensive visible light catalytic degradation RhB experiment on the samples prepared in Example 1. A 300W xenon lamp was used as the simulated light source, and a filter was placed in front to filter out short-wavelength The visible light spectrum is kept under 420nm ultraviolet light, and the RhB solution with a concentration of 10mg/L is used to simulate the sewage water body containing organic pollutants. The degradation effects of the prepared HTN, BiOCl and BHT are mainly compared. The added content of the photocatalyst is 100mg, before the light, carry out the dark adsorption reaction, in order to achieve full contact between the catalyst and the target molecule, the adsorption saturation state, after the light starts, the photocatalytic reaction is carried out in a commercially available double-layer beaker as a condensation device (as shown in Figure 6) , the purpose is to remove the influence of thermal effect on the catalytic performance during the illumination process, a group of samples are taken at intervals of 15 minutes, and the photocatalytic performance of the catalyst is characterized by the change of the concentration of the target solution RhB solution through the liquid ultraviolet test. It can be seen from Figure 3 that the catalytic effect of the composite is significantly better than that of the single component. UV-visible light spectroscopy was used to measure the concentration change of RhB solution at regular intervals. It can be seen from Figure 4 that the complex BHT catalyzes the degradation of RhB solution under visible light, and the concentration of RhB solution gradually decreases with the increase of photocatalysis time.
进一步地，为了探究实施例1中所制备的BHT样品的稳定性，本试验例利用再循环收集光催化剂，采用一种由砂芯漏斗，外接真空泵，以及微孔径0.45μm的水性滤膜组成的循环装置，将每次循环反应后的的溶液置于砂芯漏斗中，开启真空泵，抽除过滤去反应溶液，固体催化剂在滤膜处收集并进行下一组循环，从而得到在可见光照射下降解RhB，研究了BHT的光降解稳定性结果。如图5所示，可以清楚地看出，在重复实验3次后，光催化剂没有明显的失活，并且在收集过程中不可避免的催化剂的损耗，其催化性能的下降程度也未出现变化，说明所制备的层状BHT复合光催化材料表现出优异的稳定性和去除RhB的活性。Further, in order to explore the stability of the BHT sample prepared in Example 1, this test example uses recycling to collect photocatalysts, using a sand core funnel, an external vacuum pump, and a water-based filter membrane with a micropore diameter of 0.45 μm. Circulation device, put the solution after each cycle of reaction in the sand core funnel, turn on the vacuum pump, pump out and filter the reaction solution, the solid catalyst is collected at the filter membrane and undergoes the next set of cycles, so that it can be degraded under visible light irradiation RhB, the photodegradation stability results of BHT were studied. As shown in Figure 5, it can be clearly seen that after repeating the
综上所述，本发明实施例的二维层状氯氧铋和钛铌酸盐复合光催化材料的制备方法，采用高温固相法制备层状CsTi2NbO7作为前驱体，通过酸化支撑剥离H+重组得到HTN纳米片悬浮液，与BiOCl复合水热反应，成功合成了新型层状-层状BiOCl/HTN纳米片(BHT)复合异质结。该制备方法所制备复合材料可见光响应强，光催化效率高，对RhB具有良好的降解效果。从而本发明实施例提供的层状复合光催化剂及制备方法可广泛应用于光催化降解有机污水领域。In summary, the preparation method of the two-dimensional layered bismuth oxychloride and titanium niobate composite photocatalytic material in the embodiment of the present invention uses a high-temperature solid-phase method to prepare layered CsTi2NbO7 as a precursor, and strips H + recombination by acidifying the support The suspension of HTN nanosheets was obtained, which was hydrothermally reacted with BiOCl composites, and a novel layered-layered BiOCl/HTN nanosheets (BHT) composite heterojunction was successfully synthesized. The composite material prepared by the preparation method has strong visible light response, high photocatalytic efficiency and good degradation effect on RhB. Therefore, the layered composite photocatalyst and the preparation method provided by the embodiments of the present invention can be widely used in the field of photocatalytic degradation of organic sewage.
以上所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叙述并非旨在限制要求保护的本发明的范围内，而不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，都属于本发明保护范围。The above-mentioned embodiments are some of the embodiments of the present invention, but not all of them. The detailed description of the embodiments of the invention is not intended to limit the scope of the invention as claimed, but rather represents 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 making creative efforts belong to the protection scope of the present invention.
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