CN109985657B - Preparation method of BiVO4/2D g-C3N4Z heterojunction photocatalyst - Google Patents

Preparation method of BiVO4/2D g-C3N4Z heterojunction photocatalyst Download PDF

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CN109985657B
CN109985657B CN201910395741.7A CN201910395741A CN109985657B CN 109985657 B CN109985657 B CN 109985657B CN 201910395741 A CN201910395741 A CN 201910395741A CN 109985657 B CN109985657 B CN 109985657B
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杨静凯
许敏
梁波
王立坤
赵洪力
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Hebei Tianda Testing Technology Co ltd
Qinhuangdao Tianda Environmental Protection Research Institute Co ltd
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Abstract

本发明公开一种BiVO4/2D g‑C3N4Z型异质结光催化剂的制备方法，具体方法为：先通过水热反应法制备BiVO4，热聚合三聚氰胺制备石墨相氮化碳(g‑C3N4)，通过热氧化剥离得到2D g‑C3N4，然后以甲醇为溶剂，通过超声辅助化学吸附法制备BiVO4/2D g‑C3N4Z型异质结光催化剂。本发明制备的BiVO4/2D g‑C3N4Z型异质结光催化剂中，2D g‑C3N4分布在BiVO4的表面形成Z型异质结结构，能够快速分离光生电子和空穴，提高光电子的寿命，减小了光生电子空穴复合率，对可见光具有良好的响应，在催化反应40min后，罗丹明B溶液的降解率可达到93.0％。该材料可用于光降解有机污染物，对环境治理具有重要的意义。

Figure 201910395741

The invention discloses a preparation method of BiVO 4 /2D g-C 3 N 4 Z-type heterojunction photocatalyst. The specific method is as follows: firstly prepare BiVO 4 by a hydrothermal reaction method, thermally polymerize melamine to prepare graphitic carbon nitride ( g-C 3 N 4 ), 2D g-C 3 N 4 was obtained by thermal oxidative exfoliation, and then BiVO 4 /2D g-C 3 N 4 Z-type heterojunction was prepared by ultrasonic-assisted chemical adsorption method using methanol as solvent catalyst. In the BiVO 4 /2D g-C 3 N 4 Z-type heterojunction photocatalyst prepared by the invention, 2D g-C 3 N 4 is distributed on the surface of BiVO 4 to form a Z-type heterojunction structure, which can quickly separate photogenerated electrons and holes, improve the life of photoelectrons, reduce the recombination rate of photogenerated electrons and holes, and have a good response to visible light. After 40 minutes of catalytic reaction, the degradation rate of Rhodamine B solution can reach 93.0%. The material can be used for photodegradation of organic pollutants, which is of great significance to environmental governance.

Figure 201910395741

Description

BiVO4/2D g-C3N4Z型异质结光催化剂的制备方法Preparation method of BiVO4/2D g-C3N4Z heterojunction photocatalyst

技术领域technical field

本发明属于光催化剂技术领域，涉及一种BiVO4/2D g-C3N4Z型异质结光催化剂的制备方法。The invention belongs to the technical field of photocatalysts, and relates to a preparation method of a BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst.

背景技术Background technique

以半导体氧化物为主体的光催化技术，凭借其自身没有污染、完成工艺简单、能够直接利用太阳能作为反应光源并可以生产清洁能源等优良特性，成为目前治理环境污染物比较有效的技术。BiVO4作为一种新型半导体材料，其带隙窄(2.40eV左右)，具有优秀的可见光响应，导带和价带位置(对比标准氢电极)适宜，是同时具有光解水产氧、还原、降解污染物能力的一种有效半导体光催化剂。然而，BiVO4光催化剂具有电荷传输能力差、复合快、吸附性差等特点，限制了其光催化活性。BiVO4与其它半导体构建恰当的复合光催化材料是提高光生电荷分离，延长光生电子-空穴对寿命有效途径之一。Photocatalytic technology with semiconductor oxide as the main body has become a more effective technology for the treatment of environmental pollutants due to its excellent characteristics such as no pollution, simple completion process, direct use of solar energy as a reaction light source and production of clean energy. As a new type of semiconductor material, BiVO 4 has a narrow band gap (about 2.40 eV), excellent visible light response, suitable conduction band and valence band position (compared to standard hydrogen electrode), and it is capable of photo-splitting water for oxygen production, reduction and degradation at the same time. An efficient semiconductor photocatalyst with contaminant capacity. However, BiVO4 photocatalysts have the characteristics of poor charge transport ability, fast recombination, and poor adsorption, which limit their photocatalytic activity. One of the effective ways to improve the separation of photogenerated charges and prolong the lifetime of photogenerated electron-hole pairs is to construct appropriate composite photocatalytic materials between BiVO 4 and other semiconductors.

g-C3N4是一种有机聚合物半导体，是由单层的氮化碳薄片层层堆叠所成的，具有与石墨稀相似的片层结构，故称之为类石墨相氮化碳。其层上的基本组成结构单元可以由三嗪环(C3N3)和七嗪环(C6N7)构成。在这两种结构单元中，C、N原子均发生sp2杂化，通过Pz轨道上孤对电子形成一个类似于苯环结构的大π键，组成一个高度离域的共轭体系。g-C3N4的导带是由C原子Pz轨道组成，其导带位置约为-1.30eV；而价带则是由N原子的Pz轨道组成，价带位置约为1.40eV， g-C3N4的带隙宽度为2.70eV。如我们所知，将BiVO4和g-C3N4光催化剂复合成异质结，可以提升光催化活性。gC 3 N 4 is an organic polymer semiconductor, which is formed by stacking single-layer carbon nitride sheets layer by layer, and has a sheet structure similar to graphene, so it is called graphite-like carbon nitride. The basic constituent structural units on its layers may be composed of a triazine ring (C 3 N 3 ) and a heptaazine ring (C 6 N 7 ). In these two structural units, both C and N atoms undergo sp 2 hybridization, and form a large π bond similar to the benzene ring structure through the lone pair of electrons in the P z orbital, forming a highly delocalized conjugated system. The conduction band of gC 3 N 4 is composed of the P z orbital of the C atom, and its conduction band position is about -1.30eV; while the valence band is composed of the P z orbital of the N atom, and the valence band position is about 1.40 eV, and the gC 3 The band gap width of N4 is 2.70 eV. As we know, combining BiVO4 and gC3N4 photocatalysts into a heterojunction can enhance the photocatalytic activity.

现有技术的制备方法，存在光生载流子由体相到表面传输距离大、光生电子空穴对的复合率高的缺点，使BiVO4和g-C3N4之间的协同作用难以有效地发挥，限制了其光催化活性的进一步提高。The preparation method of the prior art has the disadvantages of large transport distance of photogenerated carriers from bulk to surface and high recombination rate of photogenerated electron-hole pairs, making it difficult to effectively exert the synergistic effect between BiVO 4 and gC 3 N 4 , limiting the further improvement of its photocatalytic activity.

发明内容SUMMARY OF THE INVENTION

针对现有技术的不足，本发明提供一种BiVO4/2D g-C3N4Z型异质结光催化剂的制备方法，其制备的Z型异质结光催化剂能够促进电荷高效分离、具有高光催化活性，该复合光催化剂中 2D g-C3N4分布在BiVO4的表面复合形成Z型异质结结构，充分地利用两者高的氧化和还原能力，同时，热氧化剥离之后的g-C3N4导带(CB)边缘向更负的位置移动，使得光生载流子由体相到表面的传输距离减小，提高了光生电子和空穴的分离效率，有效地改善光催化性能。在环境污染控制、能源等领域具有广泛的应用前景。In view of the deficiencies of the prior art, the present invention provides a method for preparing a BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst, and the prepared Z-type heterojunction photocatalyst can promote efficient charge separation and has high photocatalytic performance. In this composite photocatalyst, 2D gC 3 N 4 is distributed on the surface of BiVO 4 to form a Z-type heterojunction structure, making full use of the high oxidation and reduction capabilities of both, and at the same time, the gC 3 N 4 after thermal oxidation stripping The conduction band (CB) edge moves to a more negative position, which reduces the transport distance of photogenerated carriers from the bulk phase to the surface, improves the separation efficiency of photogenerated electrons and holes, and effectively improves the photocatalytic performance. It has broad application prospects in the fields of environmental pollution control and energy.

本发明是这样实现的：The present invention is realized in this way:

一种BiVO4/2D g-C3N4Z型异质结光催化剂的制备方法，其具体包括以下步骤：A preparation method of BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst, which specifically comprises the following steps:

S1、采用水热反应法制备BiVO4：S1, adopt the hydrothermal reaction method to prepare BiVO 4 :

以Bi(NO3)3·5H2O为原料溶于浓度为2mol/L的HNO3溶液，充分搅拌形成A溶液；以NH4VO3为原料溶于浓度为2mol/L的NaOH溶液，充分搅拌形成B溶液；将B溶液缓慢倒入A溶液中，并不断搅拌，形成黄色混合物悬浮液，使用浓度为2mol/L的NaOH溶液调节pH值为7～9，充分搅拌后，将制备好的BiVO4前驱液倒入水热釜中进行水热反应，待反应釜冷却至室温，分别用水和乙醇洗样，烘干得到黄色的BiVO4样品；Using Bi(NO 3 ) 3 ·5H 2 O as the raw material to dissolve in the HNO 3 solution with a concentration of 2 mol/L, fully stirring to form A solution ; Stir to form B solution; slowly pour B solution into A solution, and keep stirring to form a yellow mixture suspension, use NaOH solution with a concentration of 2mol/L to adjust the pH value to 7-9, after fully stirring, the prepared The BiVO 4 precursor solution was poured into a hydrothermal kettle for hydrothermal reaction. After the reactor was cooled to room temperature, the samples were washed with water and ethanol respectively, and dried to obtain a yellow BiVO 4 sample;

S2、采用热聚合法制备体相g-C3N4：S2. Prepare bulk gC 3 N 4 by thermal polymerization:

将装有C3N3(NH2)3的坩埚放入马弗炉中，以4℃/min的升温速率煅烧至550℃，煅烧4h，降温至室温，研磨，所得到的样品为体相g-C3N4；Put the crucible containing C 3 N 3 (NH 2 ) 3 into a muffle furnace, calcined at a heating rate of 4 ℃/min to 550 ℃, calcined for 4 h, cooled to room temperature, and ground, and the obtained sample was in bulk gC 3 N 4 ;

S3、热剥离得到2D g-C3N4：S3, thermal stripping to obtain 2D gC 3 N 4 :

取步骤S2制得的体相g-C3N4在空气气氛下进行热剥离，以升温速率4～5℃/min在550℃下煅烧2～4h，得到2D g-C3N4；The bulk gC 3 N 4 obtained in step S2 is thermally stripped under an air atmosphere, and calcined at a heating rate of 4-5° C./min at 550° C. for 2-4 hours to obtain 2D gC 3 N 4 ;

S4、采用超声辅助化学吸附法制备BiVO4/2D g-C3N4Z型异质结光催化剂：S4. Preparation of BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst by ultrasonic-assisted chemical adsorption method:

将2D g-C3N4分散在甲醇溶液中，室温下进行超声反应，之后，加入BiVO4，继续超声1h，并在通风橱中搅拌24h，甲醇挥发后，收集所得产物并在60℃下干燥12h，得到BiVO4/2Dg-C3N4 Z型异质结光催化剂。The 2D gC 3 N 4 was dispersed in methanol solution, and the ultrasonic reaction was carried out at room temperature. After that, BiVO 4 was added, continued to be sonicated for 1 h, and stirred in a fume hood for 24 h. After the methanol evaporated, the obtained product was collected and dried at 60 °C for 12 h. , the BiVO 4 /2Dg-C 3 N 4 Z-type heterojunction photocatalyst was obtained.

优选地，步骤S1中加入的Bi(NO3)3·5H2O与NH4VO3摩尔比为1:1。Preferably, the molar ratio of Bi(NO 3 ) 3 ·5H 2 O to NH 4 VO 3 added in step S1 is 1:1.

优选地，步骤S1中水热反应是在180℃下反应12h，烘干的温度为80℃，烘干时间为6-12h。Preferably, in step S1, the hydrothermal reaction is performed at 180° C. for 12 hours, the drying temperature is 80° C., and the drying time is 6-12 hours.

优选地，步骤S3中控制热剥离得到的2D g-C3N4质量为热剥离前体相g-C3N4质量的4％～6％。Preferably, the mass of the 2D gC 3 N 4 obtained by controlling the thermal exfoliation in step S3 is 4% to 6% of the mass of the thermal exfoliation precursor phase gC 3 N 4 .

优选地，步骤S4中超声反应的时间为1～2h，超声功率为100～150W。Preferably, in step S4, the time of the ultrasonic reaction is 1-2 hours, and the ultrasonic power is 100-150W.

优选地，步骤S4中2D g-C3N4加入量与甲醇加入量的关系为10mg～90mg/100mL。Preferably, the relationship between the amount of 2D gC 3 N 4 added and the amount of methanol added in step S4 is 10 mg-90 mg/100 mL.

优选地，步骤S4中BiVO4加入量与2D g-C3N4加入量的质量比为(0.1～10):1。Preferably, in step S4, the mass ratio of the added amount of BiVO 4 to the added amount of 2D gC 3 N 4 is (0.1-10):1.

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:

本发明的BiVO4/2D g-C3N4Z型异质结光催化剂的制备方法简单、易于操作、成本低，且环境友好。制备的Z型异质结光催化剂能够促进电荷高效分离、具有高光催化活性，该光催化剂中 2D g-C3N4分布在BiVO4的表面复合形成Z型异质结结构，充分地利用两者高的氧化和还原能力，同时，热氧化剥离之后的g-C3N4导带(CB)边缘向更负的位置移动，使得光生载流子由体相到表面的传输距离减小，提高了光生电子和空穴的分离效率，使其具有快速的光生电子-空穴分离效果和电子迁移能力，提高光电子的寿命，使复合光催化剂具有更加高效的光催化活性。在环境污染控制、能源等领域具有广泛的应用前景。The preparation method of the BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst of the present invention is simple, easy to operate, low in cost, and environmentally friendly. The prepared Z-type heterojunction photocatalyst can promote the efficient separation of charges and has high photocatalytic activity. The 2D gC3N4 in the photocatalyst is distributed on the surface of BiVO4 to form a Z-type heterojunction structure. At the same time, the conduction band (CB) edge of gC 3 N 4 after thermal oxidative stripping moves to a more negative position, which reduces the transport distance of photogenerated carriers from the bulk phase to the surface and improves the photogenerated electrons. And the separation efficiency of holes makes it have fast photogenerated electron-hole separation effect and electron migration ability, improve the life of photoelectrons, and make the composite photocatalyst have more efficient photocatalytic activity. It has broad application prospects in the fields of environmental pollution control and energy.

附图说明Description of drawings

图1为实施例1所制备的BiVO4、2D g-C3N4和BiVO4/2D g-C3N4Z型异质结光催化剂的XRD 图谱；1 is the XRD patterns of BiVO 4 , 2D gC 3 N 4 and BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalysts prepared in Example 1;

图2是实施例1所制备的BiVO4/2D g-C3N4Z型异质结光催化剂的SEM图；2 is a SEM image of the BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst prepared in Example 1;

图3是实施例1所制备的BiVO4/2D g-C3N4Z型异质结光催化剂的高分辨图；3 is a high-resolution image of the BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst prepared in Example 1;

图4是实施例1所制备的BiVO4、2D g-C3N4和BiVO4/2D g-C3N4Z型异质结光催化剂在可见光照射下降解罗丹明B的效果图；4 is a diagram showing the degradation of Rhodamine B by the BiVO 4 , 2D gC 3 N 4 and BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalysts prepared in Example 1 under visible light irradiation;

图5a是实施例1所制备的BiVO4、2D g-C3N4和BiVO4/2D g-C3N4Z型异质结光催化剂的电子自旋共振图；Fig. 5a is the electron spin resonance diagram of BiVO 4 , 2D gC 3 N 4 and BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst prepared in Example 1;

图5b是实施例1所制备的BiVO4、2D g-C3N4和BiVO4/2D g-C3N4Z型异质结光催化剂的电子自旋共振图。5b is the electron spin resonance diagram of BiVO 4 , 2D gC 3 N 4 and BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalysts prepared in Example 1. FIG.

具体实施方式Detailed ways

以下将结合附图详细说明本发明的示例性实施例、特征和性能方面。Exemplary embodiments, features and performance aspects of the present invention will be described in detail below with reference to the accompanying drawings.

本发明提供一种BiVO4/2D g-C3N4Z型异质结光催化剂的制备方法，先通过水热反应法制备 BiVO4，热聚合三聚氰胺制备石墨相氮化碳(g-C3N4)，通过热氧化剥离得到2D g-C3N4，然后以甲醇为溶剂，通过超声辅助化学吸附法制备BiVO4/2D g-C3N4Z型异质结光催化剂，其具体步骤为：The invention provides a preparation method of BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst. First, BiVO 4 is prepared by a hydrothermal reaction method, and graphitic carbon nitride (gC 3 N 4 ) is prepared by thermally polymerizing melamine. 2D gC 3 N 4 was obtained by thermal oxidative exfoliation, and then the BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst was prepared by ultrasonic-assisted chemical adsorption using methanol as a solvent. The specific steps are as follows:

S1、采用水热反应法制备BiVO4：S1, adopt the hydrothermal reaction method to prepare BiVO 4 :

以Bi(NO3)3·5H2O为原料溶于浓度为2mol/L的HNO3溶液，充分搅拌形成A溶液；以NH4VO3为原料溶于浓度为2mol/L的NaOH溶液，充分搅拌形成B溶液；Bi(NO3)3·5H2O与NH4VO3摩尔比为1:1；将B溶液缓慢倒入A溶液中，并不断搅拌，形成黄色混合物悬浮液，使用浓度为2mol/L的NaOH溶液调节pH值为7～9，充分搅拌后，将制备好的BiVO4前驱液倒入水热釜中在180℃下反应12h进行水热反应，待反应釜冷却至室温，分别用水和乙醇洗样后进行烘干，烘干的温度为80℃，烘干时间为6-12h，得到黄色的BiVO4样品；Using Bi(NO 3 ) 3 ·5H 2 O as the raw material to dissolve in the HNO 3 solution with a concentration of 2 mol/L, fully stirring to form A solution ; Stir to form B solution; the molar ratio of Bi(NO 3 ) 3 ·5H 2 O to NH 4 VO 3 is 1:1; slowly pour B solution into A solution, and keep stirring to form a yellow mixture suspension, the concentration of which is used is The pH value of 2mol/L NaOH solution was adjusted to 7~9. After fully stirring, the prepared BiVO 4 precursor solution was poured into a hydrothermal kettle and reacted at 180 ° C for 12 h for hydrothermal reaction. After the reaction kettle was cooled to room temperature, Wash the samples with water and ethanol, respectively, and then dry them. The drying temperature is 80 °C and the drying time is 6-12 h to obtain a yellow BiVO 4 sample;

S2、采用热聚合法制备体相g-C3N4：S2. Prepare bulk gC 3 N 4 by thermal polymerization:

将装有C3N3(NH2)3的坩埚放入马弗炉中，以4℃/min的升温速率煅烧至550℃，煅烧4h，降温至室温，研磨，所得到的样品为体相g-C3N4；Put the crucible containing C 3 N 3 (NH 2 ) 3 into a muffle furnace, calcined at a heating rate of 4 ℃/min to 550 ℃, calcined for 4 h, cooled to room temperature, and ground, and the obtained sample was in bulk gC 3 N 4 ;

S3、热剥离得到2D g-C3N4：S3, thermal stripping to obtain 2D gC 3 N 4 :

取步骤S2制得的体相g-C3N4在空气气氛下进行热剥离，以升温速率4～5℃/min在550℃下煅烧2～4h，得到2D g-C3N4，控制热剥离得到的2D g-C3N4质量为热剥离前体相g-C3N4质量的4％～6％，达到最佳热剥离效果；Take the bulk gC 3 N 4 obtained in step S2 for thermal exfoliation in an air atmosphere, and calcinate at 550 C for 2 to 4 hours at a heating rate of 4 to 5 ° C/min to obtain 2D gC 3 N 4 . The mass of 2D gC 3 N 4 is 4% to 6% of the mass of the thermal exfoliation precursor phase gC 3 N 4 to achieve the best thermal exfoliation effect;

S4、采用超声辅助化学吸附法制备BiVO4/2D g-C3N4Z型异质结光催化剂：S4. Preparation of BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst by ultrasonic-assisted chemical adsorption method:

将2D g-C3N4分散在含有甲醇的烧杯中，2D g-C3N4加入量与甲醇加入量的关系为10mg～90 mg/100mL，室温下进行超声反应，超声反应的时间为1～2h，超声功率为100～150W，之后，加入BiVO4，继续超声1h，并在通风橱中搅拌24h，甲醇挥发后，收集所得产物并在60℃下干燥12h，得到BiVO4/2D g-C3N4Z型异质结光催化剂。Disperse 2D gC 3 N 4 in a beaker containing methanol, the relationship between the amount of 2D gC 3 N 4 and the amount of methanol added is 10 mg to 90 mg/100 mL, and the ultrasonic reaction is carried out at room temperature. The time of ultrasonic reaction is 1 to 2 h, The ultrasonic power is 100-150W, after that, add BiVO 4 , continue to sonicate for 1 hour, and stir in a fume hood for 24 hours. After the methanol evaporates, the obtained product is collected and dried at 60°C for 12 hours to obtain BiVO 4 /2D gC 3 N 4 Z type heterojunction photocatalyst.

实施例1Example 1

S1、采用水热反应法制备BiVO4：S1, adopt the hydrothermal reaction method to prepare BiVO 4 :

称取0.58g硝酸铋(Bi(NO3)3·5H2O)溶于10mL的浓度为2mol/L的HNO3溶液中，充分搅拌30min后形成A溶液。称取0.14g偏钒酸铵(NH4VO3)溶于10mL的浓度为2mol/L的NaOH 溶液，充分搅拌30min后形成B溶液。将B溶液缓慢倒入A溶液中，并不断搅拌，形成黄色混合物悬浮液，使用NaOH溶液调节pH值为7，之后充分搅拌30min，将制备好的BiVO4前驱液倒入水热釜中，将水热釜拧紧密封后放入180℃烘箱中水热12h，待反应釜冷却至室温，用水和乙醇洗样，取下层黄色沉淀，80℃烘干6h得到黄色BiVO4样品；0.58 g of bismuth nitrate (Bi(NO 3 ) 3 ·5H 2 O) was weighed and dissolved in 10 mL of HNO 3 solution with a concentration of 2 mol/L, and the solution A was formed after fully stirring for 30 min. 0.14 g of ammonium metavanadate (NH 4 VO 3 ) was weighed and dissolved in 10 mL of NaOH solution with a concentration of 2 mol/L, and the solution B was formed after fully stirring for 30 min. Slowly pour the B solution into the A solution, and keep stirring to form a yellow mixture suspension. Use NaOH solution to adjust the pH value to 7, and then fully stir for 30 min. Pour the prepared BiVO 4 precursor solution into the hydrothermal kettle. The hydrothermal kettle was tightly sealed and placed in a 180°C oven for 12h. After the reaction kettle was cooled to room temperature, the samples were washed with water and ethanol, the lower yellow precipitate was removed, and dried at 80°C for 6h to obtain a yellow BiVO 4 sample;

S2、采用热聚合法制备体相g-C3N4：S2. Prepare bulk gC 3 N 4 by thermal polymerization:

将装有1g三聚氰胺的坩埚放入马弗炉中，以4℃/min的升温速率煅烧至550℃，煅烧4h，降温至室温，研磨，所得到的样品为体相g-C3N4。The crucible containing 1g of melamine was put into a muffle furnace, calcined to 550°C at a heating rate of 4°C/min, calcined for 4 hours, cooled to room temperature, and ground. The obtained sample was bulk gC 3 N 4 .

S3、热剥离得到2D g-C3N4：S3, thermal stripping to obtain 2D gC 3 N 4 :

将得到的体相g-C3N4在空气气氛下，放入马弗炉中，以4℃/min的升温速率煅烧至550℃，煅烧2h，得到2D g-C3N4；The obtained bulk gC 3 N 4 is placed in a muffle furnace under an air atmosphere, and calcined at a heating rate of 4 ℃/min to 550 ℃, and calcined for 2 hours to obtain 2D gC 3 N 4 ;

S4、采用超声辅助化学吸附法制备BiVO4/2D g-C3N4Z型异质结光催化剂：S4. Preparation of BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst by ultrasonic-assisted chemical adsorption method:

将50mg2D g-C3N4分散在含有100mL甲醇的烧杯中，将烧杯置于超声波浴中1h以获得均匀的g-C3N4分散体。之后，加入50mgBiVO4，继续超声1h，并在通风橱中搅拌24h。甲醇挥发后，收集所得产物并在60℃下干燥12h，得到BiVO4/2D g-C3N4Z型异质结光催化剂。50 mg of 2D gC3N4 was dispersed in a beaker containing 100 mL of methanol, and the beaker was placed in an ultrasonic bath for 1 h to obtain a homogeneous gC3N4 dispersion . After that, 50 mg BiVO 4 was added, sonication was continued for 1 h, and stirring was performed in a fume hood for 24 h. After methanol was evaporated, the obtained product was collected and dried at 60 °C for 12 h to obtain BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst.

图1是实施例1所制备的BiVO4、2D g-C3N4和BiVO4/2D g-C3N4Z型异质结光催化剂的XRD 图谱，图谱中的BiVO4衍射峰与BiVO4的单斜晶相(JCPDSNo.14-0688)相对应，而且特征衍射峰尖锐，表明该方法制备的样品为结晶性良好单斜相BiVO4。图谱中的2D g-C3N4位于27.46°和 21.60°的两个衍射峰分别归属于2D g-C3N4(JCPDSNo.87-1526)的(002)和(100)晶面，这是氮化碳的层层堆叠和三嗪环平面内的规则排列特征。对于制备的BiVO4/2D g-C3N4Z型异质结光催化剂的XRD图谱，图谱中包含了单斜相BiVO4和2D g-C3N4的所有衍射峰，表明复合材料只由BiVO4和2D g-C3N4两种物质组成，没有其它杂质存在。Fig. 1 is the XRD patterns of BiVO 4 , 2D gC 3 N 4 and BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalysts prepared in Example 1, the BiVO 4 diffraction peaks in the pattern and the monoclinic of BiVO 4 The crystal phase (JCPDS No. 14-0688) corresponds, and the characteristic diffraction peak is sharp, indicating that the sample prepared by this method is a monoclinic BiVO 4 with good crystallinity. The two diffraction peaks of 2D gC 3 N 4 at 27.46° and 21.60° in the spectrum are assigned to the (002) and (100) crystal planes of 2D gC 3 N 4 (JCPDSNo.87-1526), which are carbon nitride The layer-by-layer stacking and regular arrangement features in the triazine ring plane. For the XRD patterns of the as-prepared BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalysts, all diffraction peaks of the monoclinic BiVO 4 and 2D gC 3 N 4 are included in the pattern, indicating that the composite is composed of only BiVO 4 and 2D gC 3 N 4 . 2D gC 3 N 4 is composed of two substances, and no other impurities exist.

图2是实施例1所制备的BiVO4/2D g-C3N4Z型异质结光催化剂的SEM图谱，具有片状结构的2D g-C3N4分布在BiVO4颗粒上，说明两者已经复合形成Z型异质结结构。Figure 2 is the SEM image of the BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst prepared in Example 1. The 2D gC 3 N 4 with a sheet-like structure is distributed on the BiVO 4 particles, indicating that the two have been compounded A Z-type heterojunction structure is formed.

图3是实施例1所制备的BiVO4/2D g-C3N4Z型异质结光催化剂的高分辨图谱，图谱中晶面间距大约为0.309nm对应着BiVO4的(121)晶面。相比之下，与BiVO4紧密相连的结晶度较弱，晶格模糊的区域属于2D g-C3N4相。表明BiVO4与2D g-C3N4形成紧密的界面。从理论上讲，这种紧密界面可以作为载流子通道，有利于载流子转移，提高光催化性能。3 is a high-resolution map of the BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst prepared in Example 1. The interplanar spacing in the map is about 0.309 nm, which corresponds to the (121) crystal plane of BiVO 4 . In contrast, the crystallinity closely linked to BiVO 4 is weak, and the region with ambiguity of the lattice belongs to the 2D gC 3 N 4 phase. It is shown that BiVO 4 forms a tight interface with 2D gC 3 N 4 . Theoretically, this tight interface can act as a carrier channel, which is beneficial to carrier transfer and enhances the photocatalytic performance.

图4是实施例1所制备的BiVO4、2D g-C3N4和BiVO4/2D g-C3N4Z型异质结光催化剂在可见光照射下降解罗丹明B的效果图。图中A区域为黑暗环境，B区域为可见光照射，从可见光照射开始计时，BiVO4/2D g-C3N4Z型异质结在催化反应40min后，罗丹明B溶液的降解率已达到 93.0％，说明BiVO4/2D g-C3N4Z型异质结在可见光下具有优异的光催化活性。而且，从图中对比可知，BiVO4/2D g-C3N4Z型异质结的光催化活性明显优于BiVO4和2D g-C3N4。FIG. 4 is a diagram showing the degradation of Rhodamine B by the BiVO 4 , 2D gC 3 N 4 and BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalysts prepared in Example 1 under visible light irradiation. In the figure, area A is in the dark environment, and area B is illuminated by visible light. From the time of visible light illumination, the degradation rate of rhodamine B solution has reached 93.0% after the catalytic reaction of BiVO 4 /2D gC 3 N 4 Z-type heterojunction for 40 minutes. , indicating that the BiVO 4 /2D gC 3 N 4 Z-type heterojunction has excellent photocatalytic activity under visible light. Moreover, it can be seen from the comparison in the figure that the photocatalytic activity of BiVO 4 /2D gC 3 N 4 Z-type heterojunction is obviously better than that of BiVO 4 and 2D gC 3 N 4 .

图5a和图5b是实施例1所制备的BiVO4、2D g-C3N4和BiVO4/2D g-C3N4Z型异质结光催化剂的电子自旋共振图。表明·O2-和·OH是光催化过程中的主要活性物种。此外，结合BiVO4和 2D g-C3N4的能带结构，证明了形成的BiVO4/2D g-C3N4Z型异质结。5a and 5b are electron spin resonance diagrams of BiVO 4 , 2D gC 3 N 4 and BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalysts prepared in Example 1. It is shown that · O2- and ·OH are the main active species in the photocatalytic process. Furthermore, combining the band structures of BiVO4 and 2D gC3N4 , the formed BiVO4 /2D gC3N4 Z - type heterojunction is demonstrated .

实施例2Example 2

S1、采用水热反应法制备BiVO4：S1, adopt the hydrothermal reaction method to prepare BiVO 4 :

称取0.58g硝酸铋(Bi(NO3)3·5H2O)溶于10mL的浓度为2mol/L的HNO3溶液中，充分搅拌30min后形成A溶液。称取0.14g偏钒酸铵(NH4VO3)溶于10mL的浓度为2mol/L的NaOH 溶液，充分搅拌30min后形成B溶液。将B溶液缓慢倒入A溶液中，并不断搅拌，形成黄色混合物悬浮液，使用NaOH溶液调节pH值为7，之后充分搅拌30min，将制备好的BiVO4前驱液倒入水热釜中，将水热釜拧紧密封后放入180℃烘箱中水热12h，待反应釜冷却至室温，用水和乙醇洗样，取下层黄色沉淀，80℃烘干6h得到黄色BiVO4样品；0.58 g of bismuth nitrate (Bi(NO 3 ) 3 ·5H 2 O) was weighed and dissolved in 10 mL of HNO 3 solution with a concentration of 2 mol/L, and the solution A was formed after fully stirring for 30 min. 0.14 g of ammonium metavanadate (NH 4 VO 3 ) was weighed and dissolved in 10 mL of NaOH solution with a concentration of 2 mol/L, and the solution B was formed after fully stirring for 30 min. Slowly pour the B solution into the A solution, and keep stirring to form a yellow mixture suspension. Use NaOH solution to adjust the pH value to 7, and then fully stir for 30 min. Pour the prepared BiVO 4 precursor solution into the hydrothermal kettle. The hydrothermal kettle was tightly sealed and placed in a 180°C oven for 12h. After the reaction kettle was cooled to room temperature, the samples were washed with water and ethanol, the lower yellow precipitate was removed, and dried at 80°C for 6h to obtain a yellow BiVO 4 sample;

S2、采用热聚合法制备体相g-C3N4：S2. Prepare bulk gC 3 N 4 by thermal polymerization:

将装有1g三聚氰胺的坩埚放入马弗炉中，以4℃/min的升温速率煅烧至550℃，煅烧2h，降温至室温，研磨，所得到的样品为体相g-C3N4。The crucible containing 1g of melamine was put into a muffle furnace, calcined to 550°C at a heating rate of 4°C/min, calcined for 2 hours, cooled to room temperature, and ground. The obtained sample was bulk gC 3 N 4 .

S3、热剥离得到2D g-C3N4：S3, thermal stripping to obtain 2D gC 3 N 4 :

将得到的体相g-C3N4在空气气氛下，放入马弗炉中，以4℃/min的升温速率煅烧至550℃，煅烧2h，得到2D g-C3N4；The obtained bulk gC 3 N 4 is placed in a muffle furnace under an air atmosphere, and calcined at a heating rate of 4 ℃/min to 550 ℃, and calcined for 2 hours to obtain 2D gC 3 N 4 ;

S4、采用超声辅助化学吸附法制备BiVO4/2D g-C3N4Z型异质结光催化剂：S4. Preparation of BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst by ultrasonic-assisted chemical adsorption method:

将10mg2D g-C3N4分散在含有100mL甲醇的烧杯中，将烧杯置于超声波浴中1h以获得均匀的g-C3N4分散体。之后，加入90mgBiVO4，继续超声1h，并在通风橱中搅拌24h。甲醇挥发后，收集所得产物并在60℃下干燥12h，得到BiVO4/2D g-C3N4Z型异质结光催化剂。 10 mg of 2D gC3N4 was dispersed in a beaker containing 100 mL of methanol, and the beaker was placed in an ultrasonic bath for 1 h to obtain a homogeneous gC3N4 dispersion. After that, 90 mg BiVO4 was added, sonication was continued for 1 h, and stirring was performed in a fume hood for 24 h. After methanol was evaporated, the obtained product was collected and dried at 60 °C for 12 h to obtain BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst.

实施例3Example 3

S1、采用水热反应法制备BiVO4：S1, adopt the hydrothermal reaction method to prepare BiVO 4 :

称取0.58g硝酸铋(Bi(NO3)3·5H2O)溶于10mL的浓度为2mol/L的HNO3溶液中，充分搅拌30min后形成A溶液。称取0.14g偏钒酸铵(NH4VO3)溶于10mL的浓度为2mol/L的NaOH 溶液，充分搅拌30min后形成B溶液。将B溶液缓慢倒入A溶液中，并不断搅拌，形成黄色混合物悬浮液，使用NaOH溶液调节pH值为7，之后充分搅拌30min，将制备好的BiVO4前驱液倒入水热釜中，将水热釜拧紧密封后放入180℃烘箱中水热12h，待反应釜冷却至室温，用水和乙醇洗样，取下层黄色沉淀，80℃烘干6h得到黄色BiVO4样品；0.58 g of bismuth nitrate (Bi(NO 3 ) 3 ·5H 2 O) was weighed and dissolved in 10 mL of HNO 3 solution with a concentration of 2 mol/L, and the solution A was formed after fully stirring for 30 min. 0.14 g of ammonium metavanadate (NH 4 VO 3 ) was weighed and dissolved in 10 mL of NaOH solution with a concentration of 2 mol/L, and the solution B was formed after fully stirring for 30 min. Slowly pour the B solution into the A solution, and keep stirring to form a yellow mixture suspension. Use NaOH solution to adjust the pH value to 7, and then fully stir for 30 min. Pour the prepared BiVO 4 precursor solution into the hydrothermal kettle. The hydrothermal kettle was tightly sealed and placed in a 180°C oven for 12h. After the reaction kettle was cooled to room temperature, the samples were washed with water and ethanol, the lower yellow precipitate was removed, and dried at 80°C for 6h to obtain a yellow BiVO 4 sample;

S2、采用热聚合法制备体相g-C3N4：S2. Prepare bulk gC 3 N 4 by thermal polymerization:

将装有1g三聚氰胺的坩埚放入马弗炉中，以4℃/min的升温速率煅烧至550℃，煅烧4h，降温至室温，研磨，所得到的样品为体相g-C3N4。The crucible containing 1g of melamine was put into a muffle furnace, calcined to 550°C at a heating rate of 4°C/min, calcined for 4 hours, cooled to room temperature, and ground. The obtained sample was bulk gC 3 N 4 .

S3、热剥离得到2D g-C3N4：S3, thermal stripping to obtain 2D gC 3 N 4 :

将得到的体相g-C3N4在空气气氛下，放入马弗炉中，以4℃/min的升温速率煅烧至550℃，煅烧2h，得到2D g-C3N4；The obtained bulk gC 3 N 4 is placed in a muffle furnace under an air atmosphere, and calcined at a heating rate of 4 ℃/min to 550 ℃, and calcined for 2 hours to obtain 2D gC 3 N 4 ;

S4、采用超声辅助化学吸附法制备BiVO4/2D g-C3N4Z型异质结光催化剂：S4. Preparation of BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst by ultrasonic-assisted chemical adsorption method:

将30mg2D g-C3N4分散在含有100mL甲醇的烧杯中，将烧杯置于超声波浴中1h以获得均匀的g-C3N4分散体。之后，加入70mgBiVO4，继续超声1h，并在通风橱中搅拌24h。甲醇挥发后，收集所得产物并在60℃下干燥12h，得到BiVO4/2D g-C3N4Z型异质结光催化剂。30 mg of 2D gC3N4 was dispersed in a beaker containing 100 mL of methanol, and the beaker was placed in an ultrasonic bath for 1 h to obtain a homogeneous gC3N4 dispersion . After that, 70 mg of BiVO4 was added, sonication was continued for 1 h, and stirred in a fume hood for 24 h. After methanol was evaporated, the obtained product was collected and dried at 60 °C for 12 h to obtain BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst.

实施例4Example 4

S1、采用水热反应法制备BiVO4：S1, adopt the hydrothermal reaction method to prepare BiVO 4 :

称取0.58g硝酸铋(Bi(NO3)3·5H2O)溶于10mL的浓度为2mol/L的HNO3溶液中，充分搅拌30min后形成A溶液。称取0.14g偏钒酸铵(NH4VO3)溶于10mL的浓度为2mol/L的NaOH 溶液，充分搅拌30min后形成B溶液。将B溶液缓慢倒入A溶液中，并不断搅拌，形成黄色混合物悬浮液，使用NaOH溶液调节pH值为7，之后充分搅拌30min，将制备好的BiVO4前驱液倒入水热釜中，将水热釜拧紧密封后放入180℃烘箱中水热12h，待反应釜冷却至室温，用水和乙醇洗样，取下层黄色沉淀，80℃烘干6h得到黄色BiVO4样品；0.58 g of bismuth nitrate (Bi(NO 3 ) 3 ·5H 2 O) was weighed and dissolved in 10 mL of HNO 3 solution with a concentration of 2 mol/L, and the solution A was formed after fully stirring for 30 min. 0.14 g of ammonium metavanadate (NH 4 VO 3 ) was weighed and dissolved in 10 mL of NaOH solution with a concentration of 2 mol/L, and the solution B was formed after fully stirring for 30 min. Slowly pour the B solution into the A solution, and keep stirring to form a yellow mixture suspension. Use NaOH solution to adjust the pH value to 7, and then fully stir for 30 min. Pour the prepared BiVO 4 precursor solution into the hydrothermal kettle. The hydrothermal kettle was tightly sealed and placed in a 180°C oven for 12h. After the reaction kettle was cooled to room temperature, the samples were washed with water and ethanol, the lower yellow precipitate was removed, and dried at 80°C for 6h to obtain a yellow BiVO 4 sample;

S2、采用热聚合法制备体相g-C3N4：S2. Prepare bulk gC 3 N 4 by thermal polymerization:

将装有1g三聚氰胺的坩埚放入马弗炉中，以4℃/min的升温速率煅烧至550℃，煅烧4h，降温至室温，研磨，所得到的样品为体相g-C3N4。The crucible containing 1g of melamine was put into a muffle furnace, calcined to 550°C at a heating rate of 4°C/min, calcined for 4 hours, cooled to room temperature, and ground. The obtained sample was bulk gC 3 N 4 .

S3、热剥离得到2D g-C3N4：S3, thermal stripping to obtain 2D gC 3 N 4 :

将得到的体相g-C3N4在空气气氛下，放入马弗炉中，以4℃/min的升温速率煅烧至550℃，煅烧2h，得到2D g-C3N4；The obtained bulk gC 3 N 4 is placed in a muffle furnace under an air atmosphere, and calcined at a heating rate of 4 ℃/min to 550 ℃, and calcined for 2 hours to obtain 2D gC 3 N 4 ;

S4、采用超声辅助化学吸附法制备BiVO4/2D g-C3N4Z型异质结光催化剂：S4. Preparation of BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst by ultrasonic-assisted chemical adsorption method:

将70mg2D g-C3N4分散在含有100mL甲醇的烧杯中，将烧杯置于超声波浴中1h以获得均匀的g-C3N4分散体。之后，加入30mgBiVO4，继续超声1h，并在通风橱中搅拌24h。甲醇挥发后，收集所得产物并在60℃下干燥12h，得到BiVO4/2D g-C3N4Z型异质结光催化剂。70 mg of 2D gC3N4 was dispersed in a beaker containing 100 mL of methanol, and the beaker was placed in an ultrasonic bath for 1 h to obtain a homogeneous gC3N4 dispersion . After that, 30 mg BiVO4 was added, sonication was continued for 1 h, and stirring was performed in a fume hood for 24 h. After methanol was evaporated, the obtained product was collected and dried at 60 °C for 12 h to obtain BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst.

实施例5Example 5

S1、采用水热反应法制备BiVO4：S1, adopt the hydrothermal reaction method to prepare BiVO 4 :

称取0.58g硝酸铋(Bi(NO3)3·5H2O)溶于10mL的浓度为2mol/L的HNO3溶液中，充分搅拌30min后形成A溶液。称取0.14g偏钒酸铵(NH4VO3)溶于10mL的浓度为2mol/L的NaOH 溶液，充分搅拌30min后形成B溶液。将B溶液缓慢倒入A溶液中，并不断搅拌，形成黄色混合物悬浮液，使用NaOH溶液调节pH值为7，之后充分搅拌30min，将制备好的BiVO4前驱液倒入水热釜中，将水热釜拧紧密封后放入180℃烘箱中水热12h，待反应釜冷却至室温，用水和乙醇洗样，取下层黄色沉淀，80℃烘干6h得到黄色BiVO4样品；0.58 g of bismuth nitrate (Bi(NO 3 ) 3 ·5H 2 O) was weighed and dissolved in 10 mL of HNO 3 solution with a concentration of 2 mol/L, and the solution A was formed after fully stirring for 30 min. 0.14 g of ammonium metavanadate (NH 4 VO 3 ) was weighed and dissolved in 10 mL of NaOH solution with a concentration of 2 mol/L, and the solution B was formed after fully stirring for 30 min. Slowly pour the B solution into the A solution, and keep stirring to form a yellow mixture suspension. Use NaOH solution to adjust the pH value to 7, and then fully stir for 30 min. Pour the prepared BiVO 4 precursor solution into the hydrothermal kettle. The hydrothermal kettle was tightly sealed and placed in a 180°C oven for 12h. After the reaction kettle was cooled to room temperature, the samples were washed with water and ethanol, the lower yellow precipitate was removed, and dried at 80°C for 6h to obtain a yellow BiVO 4 sample;

S2、采用热聚合法制备体相g-C3N4：S2. Prepare bulk gC 3 N 4 by thermal polymerization:

将装有1g三聚氰胺的坩埚放入马弗炉中，以4℃/min的升温速率煅烧至550℃，煅烧4h，降温至室温，研磨，所得到的样品为体相g-C3N4；Put the crucible containing 1 g of melamine into a muffle furnace, calcined to 550 °C at a heating rate of 4 °C/min, calcined for 4 h, cooled to room temperature, and ground, the obtained sample is bulk gC 3 N 4 ;

S3、热剥离得到2D g-C3N4：S3, thermal stripping to obtain 2D gC 3 N 4 :

将得到的体相g-C3N4在空气气氛下，放入马弗炉中，以4℃/min的升温速率煅烧至550℃，煅烧2h，得到2D g-C3N4；The obtained bulk gC 3 N 4 is placed in a muffle furnace under an air atmosphere, and calcined at a heating rate of 4 ℃/min to 550 ℃, and calcined for 2 hours to obtain 2D gC 3 N 4 ;

S4、采用超声辅助化学吸附法制备BiVO4/2D g-C3N4Z型异质结光催化剂：S4. Preparation of BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst by ultrasonic-assisted chemical adsorption method:

将90mg2D g-C3N4分散在含有100mL甲醇的烧杯中，将烧杯置于超声波浴中1h以获得均匀的g-C3N4分散体。之后，加入10mgBiVO4，继续超声1h，并在通风橱中搅拌24h。甲醇挥发后，收集所得产物并在60℃下干燥12h，得到BiVO4/2D g-C3N4Z型异质结光催化剂。90 mg of 2D gC3N4 was dispersed in a beaker containing 100 mL of methanol, and the beaker was placed in an ultrasonic bath for 1 h to obtain a homogeneous gC3N4 dispersion . After that, 10 mg BiVO4 was added, sonication was continued for 1 h, and stirring was performed in a fume hood for 24 h. After methanol was evaporated, the obtained product was collected and dried at 60 °C for 12 h to obtain BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst.

综上，本发明制备的BiVO4/2D g-C3N4Z型异质结光催化剂具有更加高效的光催化活性。在环境污染控制、能源等领域具有广泛的应用前景。In conclusion, the BiVO 4 /2D gC 3 N 4 Z-type heterojunction photocatalyst prepared by the present invention has more efficient photocatalytic activity. It has broad application prospects in the fields of environmental pollution control and energy.

最后应说明的是：以上所述的各实施例仅用于说明本发明技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分或全部技术特征进行等同替换；而这些修改或替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。Finally, it should be noted that the above-described embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand: It is still possible to modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention. scope.

Claims (5)

1. BiVO4/2D g-C3N4The preparation method of the Z-type heterojunction photocatalyst is characterized by comprising the following steps: the method specifically comprises the following steps:
s1 preparation of BiVO by hydrothermal reaction method4：
With Bi (NO)3)3·5H2Dissolving O as raw material in HNO with the concentration of 2mol/L3Fully stirring the solution to form solution A; by NH4VO3Dissolving the raw materials in 2mol/L NaOH solution, and fully stirring to form solution B; slowly pouring the solution B into the solution A, continuously stirring to form a yellow mixture suspension, adjusting the pH value to 7-9 by using a NaOH solution with the concentration of 2mol/L, fully stirring, and then, adding the prepared BiVO4Pouring the precursor solution into a hydrothermal kettle for hydrothermal reaction, respectively washing the sample with water and ethanol after the reaction kettle is cooled to room temperature, and drying to obtain yellow BiVO4A sample; the hydrothermal reaction is carried out for 12 hours at 180 ℃, the drying temperature is 80 ℃, and the drying time is 6-12 hours;
s2 preparation of bulk phase g-C by thermal polymerization3N4：
Will be provided with C3N3(NH2)3Is put into the crucibleCalcining in a muffle furnace at a heating rate of 4 ℃/min to 550 ℃ for 4h, cooling to room temperature, grinding to obtain a sample of bulk phase g-C3N4；
S3, hot peeling to obtain 2D g-C3N4：
Taking the bulk phase g-C obtained in the step S23N4Performing thermal stripping in an air atmosphere, and calcining at 550 ℃ for 2-4 h at a heating rate of 4-5 ℃/min to obtain 2D g-C3N4(ii) a Obtained 2D g-C3N4Mass is thermal peeling precursor phase g-C3N44-6% of the mass;
s4 preparation of BiVO by ultrasonic-assisted chemical adsorption method4/2D g-C3N4Z-type heterojunction photocatalyst:
2D g-C3N4Dispersing in methanol solution, ultrasonic reacting at room temperature, adding BiVO4Continuing to perform ultrasonic treatment for 1h, stirring in a fume hood for 24h, volatilizing methanol, collecting the obtained product, and drying at 60 ℃ for 12h to obtain BiVO4/2D g-C3N4A Z-type heterojunction photocatalyst.
2. BiVO according to claim 14/2D g-C3N4The preparation method of the Z-type heterojunction photocatalyst is characterized by comprising the following steps: bi (NO) added in step S13)3·5H2O and NH4VO3The molar ratio is 1: 1.
3. BiVO according to claim 14/2D g-C3N4The preparation method of the Z-type heterojunction photocatalyst is characterized by comprising the following steps: in the step S4, the time of the ultrasonic reaction is 1-2 h, and the ultrasonic power is 100-150W.
4. BiVO according to claim 14/2D g-C3N4The preparation method of the Z-type heterojunction photocatalyst is characterized by comprising the following steps: 2D g-C in step S43N4The relation between the addition amount and the methanol addition amount is 10 mg-90 mg/100 mL.
5. BiVO according to claim 1 or 44/2D g-C3N4The preparation method of the Z-type heterojunction photocatalyst is characterized by comprising the following steps: BiVO in step S44The addition amount is 2D g-C3N4The mass ratio of the addition amount is (0.1-10): 1.
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