CN111889127B - In-situ growth preparation of beta-Bi 2 O 3 /g-C 3 N 4 Method for preparing nano composite photocatalyst - Google Patents

In-situ growth preparation of beta-Bi 2 O 3 /g-C 3 N 4 Method for preparing nano composite photocatalyst Download PDF

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CN111889127B
CN111889127B CN202010627280.4A CN202010627280A CN111889127B CN 111889127 B CN111889127 B CN 111889127B CN 202010627280 A CN202010627280 A CN 202010627280A CN 111889127 B CN111889127 B CN 111889127B
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CN111889127A (en
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王东波
余昕
黄琳
冯庆革
陆明东
雷烨
苏泽林
黄纤晴
黄莹
董茜苑
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Abstract

The invention discloses a method for preparing beta-Bi by in-situ growth 2 O 3 /g‑C 3 N 4 A method for preparing a nano composite photocatalyst belongs to the technical field of photocatalyst preparation. The method uses melamine and urea as raw materials, and g-C is obtained by high-temperature calcination 3 N 4 Then g-C 3 N 4 Dispersing in glycol solution dissolved with bismuth nitrate, carrying out solvent heat treatment for a certain time, cooling, washing, centrifuging, drying and the like to finally obtain the beta-Bi 2 O 3 /g‑C 3 N 4 A composite photocatalyst is provided. The nano composite photocatalyst prepared by the invention has a simple preparation process, is used for photocatalytic degradation of organic pollutants such as methyl orange, tetracycline hydrochloride and the like in sewage under visible light, and has high degradation efficiency.

Description

In-situ growth preparation of beta-Bi 2 O 3 /g-C 3 N 4 Method for preparing nano composite photocatalyst
Technical Field
The invention relates to the technical field of photocatalyst preparation, in particular to a method for preparing beta-Bi by in-situ growth 2 O 3 /g-C 3 N 4 A method for preparing a nano composite photocatalyst.
Background
Solar energy is a clean energy source which is stable in source and can be used continuously, the semiconductor photocatalysis technology can achieve the purpose of converting solar energy into chemical energy under a mild condition, and since scientists find that titanium dioxide can decompose water under ultraviolet light to produce hydrogen in 1972, the technology has been developed greatly and has attracted wide attention in the fields of hydrogen production by photolysis of water, carbon dioxide photo-reduction, organic pollutant photo-degradation, virus photo-inactivation and the like. However, in sunlight, ultraviolet light accounts for only about 4% and visible light accounts for 43%, so that it is urgent to develop a semiconductor material that can respond to visible light in order to make full use of solar energy.
Graphite phase carbon nitride g-C 3 N 4 Is an ideal visible light drive photocatalyst, has the characteristics of simple synthesis, no toxicity, stable property and the like, but is limited by the problems of weak light absorption capacity and serious photocarrier recombination, so that the g-C is formed 3 N 4 It is difficult to be practically used. Bismuth oxide is an important member of bismuth-based semiconductor materials, and has six different crystal phases, among which β -Bi 2 O 3 The forbidden band width is 2.6eV, the nanometer sheet is in a cross-linked nanometer sheet shape, and the crystal phase has narrower forbidden band width and more regular appearance compared with other crystal phases. The construction of the heterojunction is an effective method for improving the photocatalytic performance of the semiconductor material, can improve the light absorption capacity and effectively inhibit the recombination between photon-generated carriers, and the beta-Bi is constructed at present 2 O 3 /g-C 3 N 4 The reports of the heterojunction are less, the heterojunction is obtained by a method of 'presynthesizing + physical assembly', the heterojunction is not firm, and the improvement of the photocatalytic performance is limited, so that the novel preparation method is adopted to obtain the beta-Bi 2 O 3 /g-C 3 N 4 The heterojunction is very important.
Disclosure of Invention
The invention aims to provide a method for preparing beta-Bi by in-situ growth 2 O 3 /g-C 3 N 4 Method for preparing nano composite photocatalyst and beta-Bi prepared by method 2 O 3 /g-C 3 N 4 The nano composite material has visible light catalytic performance, the degradation rate of methyl orange MO solution in 2 hours can reach 99%, and the degradation rate of tetracycline hydrochloride TC-HCl solution in 2.5 hours can reach 93%.
In order to solve the technical problems, the invention provides the following technical scheme: in-situ growth preparation of beta-Bi 2 O 3 /g-C 3 N 4 The method for preparing the nano composite photocatalyst comprises the following steps:
(1) Uniformly mixing 10g of urea and melamine according to the mass ratio of 1:1-1:4, calcining for 2h at 550 ℃ in a muffle furnace, and naturally cooling to obtain blocky g-C 3 N 4 Grinding into powder for later use;
(2) Adding 50ml of ethylene glycol into 0.2500g-1.000g of bismuth nitrate, and violently stirring for 1h to completely dissolve the bismuth nitrate;
(3) 0.932g of g-C prepared in (1) was weighed 3 N 4 Adding into the mixture obtained in the step (2), stirring vigorously for 1h, and carrying out ultrasonic treatment for 30min;
(4) Transferring the mixed solution obtained in the step (3) into a polytetrafluoroethylene lining reaction kettle with the capacity of 100ml, and carrying out solvothermal reaction at the temperature of 160-200 ℃ for 8 hours;
(5) After the reaction kettle is naturally cooled to room temperature, the beta-Bi is obtained after centrifugation, washing and drying 2 O 3 /g-C 3 N 4 A nano composite photocatalyst.
The bismuth nitrate in the step (2) is Bi (NO) 3 ) 3 ·5H 2 O。
Preparation of beta-Bi by in situ growth as described in the present invention 2 O 3 /g-C 3 N 4 A preferable scheme in the method of the nano composite photocatalyst is as follows: g to C 3 N 4 Ultrasonically dispersing in glycol solution dissolved with bismuth nitrate to obtain nano composite lightbeta-Bi in the catalyst 2 O 3 And g-C 3 N 4 The mass ratio of (A) to (B) is 0.1.
Except for other descriptions, the percentages are mass percentages, and the sum of the content percentages of all the components is 100%.
The invention has the beneficial effects that:
1. beta-Bi prepared by the invention 2 O 3 For aggregated nanoplatelets, g-C is added during the preparation process 3 N 4 When is beta-Bi 2 O 3 Uniformly grow in g-C 3 N 4 Of the surface of (a).
2. In the process of photocatalytic degradation, due to beta-Bi 2 O 3 Is in g-C 3 N 4 The surface grows in situ, and the dense interface reduces the resistance of photon-generated carriers to be transmitted between the surface and the dense interface.
3、β-Bi 2 O 3 And g-C 3 N 4 The energy level structures are staggered, so that a heterojunction beneficial to separation of photon-generated carriers can be formed, and the photocatalytic performance of the composite material is promoted.
4. The beta-Bi prepared by the preparation method 2 O 3 /g-C 3 N 4 The nano composite photocatalyst has visible light catalytic performance, the degradation rate of methyl orange MO solution in 2 hours under visible light can reach 99%, and the degradation rate of tetracycline hydrochloride TC-HCl solution in 2.5 hours under visible light can reach 93%.
Drawings
FIG. 1 shows the preparation of beta-Bi by in-situ growth according to the present invention 2 O 3 /g-C 3 N 4 A process flow chart of the method of the nano composite photocatalyst.
FIG. 2 shows beta-Bi prepared in example 2 O 3 /g-C 3 N 4 XRD pattern of the nano composite photocatalyst;
FIG. 3 shows beta-Bi prepared in example 2 O 3 /g-C 3 N 4 SEM picture of the nano composite photocatalyst;
FIG. 4 shows g-C 3 N 4 、β-Bi 2 O 3 、β-Bi 2 O 3 /g-C 3 N 4 The nano composite photocatalyst is a photocatalytic degradation graph of a methyl orange solution under the irradiation of visible light.
FIG. 5 is g-C 3 N 4 、β-Bi 2 O 3 、β-Bi 2 O 3 /g-C 3 N 4 The nano composite photocatalyst is a photocatalytic degradation graph of tetracycline hydrochloride solution under the irradiation of visible light.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be embodied in other specific forms than described herein, and it will be apparent to those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the invention.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with at least one implementation of the invention is included. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
This example is the in situ growth method for preparing beta-Bi according to the present invention 2 O 3 /g-C 3 N 4 A specific example of the method for preparing the nano composite photocatalyst comprises the following steps:
(1) 5.000g of urea and 5.000g of melamine are uniformly mixed, calcined for 2 hours at 550 ℃ in a muffle furnace, and naturally cooled to obtain blocky g-C 3 N 4 Grinding into powder for later use;
(2) Taking 0.250g of bismuth nitrate, adding 50ml of ethylene glycol, and violently stirring for 1h to completely dissolve the bismuth nitrate;
(3) Weighing 0.932g of g-C in (1) 3 N 4 Adding into the mixture obtained in the step (2), stirring vigorously for 1h, and carrying out ultrasonic treatment for 30min;
(4) Transferring the mixed solution obtained in the step (3) into a polytetrafluoroethylene lining reaction kettle with the capacity of 100ml, and carrying out solvothermal reaction under the reaction condition of 160 ℃ for 8 hours;
(5) After the reaction kettle is naturally cooled to room temperature, the beta-Bi is obtained after centrifugation, washing and drying 2 O 3 /g-C 3 N 4 A nano composite photocatalyst.
The prepared beta-Bi 2 O 3 /g-C 3 N 4 The nano composite photocatalyst degrades methyl orange MO and tetracycline hydrochloride TC-HCl in water under visible light to measure the photocatalytic activity of the nano composite photocatalyst, and the degradation rate of MO within 2h reaches 99%, and the degradation rate of TC-HCl within 2.5h reaches 93%.
In the invention, the proportion of 0.250g of bismuth nitrate and 0.932g of graphite-phase carbon nitride is adopted, so that the g-C is improved 3 N 4 Light absorption ability of (b), and also makes beta-Bi 2 O 3 The growth does not excessively aggregate to occupy the active sites of the reaction.
The product obtained is beta-Bi by the characterization of X-ray powder diffraction 2 O 3 /g-C 3 N 4 . As can be seen from FIG. 2, g-C 3 N 4 And beta-Bi 2 O 3 The diffraction peaks of the crystal correspond to JCPDF #87-1526 and JCPDF #78-1793 respectively, no other impurity phases are detected, and the sharp diffraction peak shows that the prepared sample has better crystallinity.
beta-Bi from FIG. 3 2 O 3 /g-C 3 N 4 SEM picture of nano composite photocatalyst shows that the prepared beta-Bi 2 O 3 Adding g-C into a solvothermal system for uniformly dispersing the nano-sheets 3 N 4 Post, beta-Bi 2 O 3 Uniformly grow in g-C 3 N 4 A surface. In the process of photocatalytic degradation of pollutants, due to beta-Bi 2 O 3 Is grown in situ in g-C 3 N 4 The surface and interface structure is compact and ordered, which is beneficial to photo-generated carriers in beta-Bi 2 O 3 And g-C 3 N 4 To be transmitted between.
Example 2
This example is the in situ growth method for preparing beta-Bi according to the present invention 2 O 3 /g-C 3 N 4 Another specific example of the method for preparing the nano composite photocatalyst comprises the following steps:
(1) 3.333g of urea and 6.667g of melamine are mixed uniformly, calcined for 2h at 550 ℃ in a muffle furnace, and naturally cooled to obtain blocky g-C 3 N 4 Grinding into powder for later use;
(2) Taking 0.500g of bismuth nitrate, adding 50ml of ethylene glycol, and violently stirring for 1 hour to completely dissolve the bismuth nitrate;
(3) Weighing 0.932g of g-C in (1) 3 N 4 Adding into the mixture obtained in the step (2), stirring vigorously for 1h, and carrying out ultrasonic treatment for 30min;
(4) Transferring the mixed solution obtained in the step (3) into a polytetrafluoroethylene lining reaction kettle with the capacity of 100ml, and carrying out solvothermal reaction under the reaction condition of 180 ℃ for 8 hours;
(5) After the reaction kettle is naturally cooled to room temperature, centrifuging, washing and drying are carried out to obtain the beta-Bi 2 O 3 /g-C 3 N 4 A nano composite photocatalyst.
The prepared beta-Bi 2 O 3 /g-C 3 N 4 The-1 nanometer composite photocatalyst degrades methyl orange MO and tetracycline hydrochloride TC-HCl in water under visible light to measure the photocatalytic activity of the composite photocatalyst, and the degradation rate of MO within 2h reaches 83%, and the degradation rate of TC-HCl reaches 85%.
Example 3
This example is the in situ growth method for preparing beta-Bi according to the present invention 2 O 3 /g-C 3 N 4 A further specific example of the method for preparing the nanocomposite photocatalyst comprises the following steps:
(1) 2.000g of urea and 8.000g of melamine are uniformly mixed, calcined for 2 hours at 550 ℃ in a muffle furnace, and naturally cooled to obtain blocky g-C 3 N 4 Grinding into powder for later use;
(2) 1.000g of bismuth nitrate is taken, 50ml of ethylene glycol is added, and the mixture is stirred vigorously for 1 hour to ensure that the bismuth nitrate is completely dissolved;
(3) Weighing 0.932g of g-C in (1) 3 N 4 Adding into the mixture obtained in the step (2), stirring vigorously for 1h, and carrying out ultrasonic treatment for 30min;
(4) Transferring the mixed solution obtained in the step (3) into a polytetrafluoroethylene lining reaction kettle with the capacity of 100ml, and carrying out solvothermal reaction under the reaction condition of 200 ℃ for 8 hours;
(5) After the reaction kettle is naturally cooled to room temperature, the beta-Bi is obtained after centrifugation, washing and drying 2 O 3 /g-C 3 N 4 A nano composite photocatalyst.
The prepared beta-B i2 O 3 /g-C 3 N 4 And (3) degrading methyl orange MO and tetracycline hydrochloride TC-HCl in water by the-2 nano composite photocatalyst under visible light to measure the photocatalytic activity of the composite photocatalyst, and finding that the degradation rate of MO reaches 89% and the degradation rate of TC-HCl reaches 81% within 2 h.
Comparative example 1
(1) 5.000g of urea and 5.000g of melamine are uniformly mixed, calcined for 2 hours at 550 ℃ in a muffle furnace, and naturally cooled to obtain blocky g-C 3 N 4 And grinding into powder.
The prepared g-C 3 N 4 The photocatalytic material degrades methyl orange MO and tetracycline hydrochloride TC-HCl in water under visible light to measure the photocatalytic activity of the material, and the degradation rate of MO within 2h is 45%, and the degradation rate of TC-HCl is 34%.
Comparative example 2
(1) Taking 0.500g of bismuth nitrate, adding 50ml of ethylene glycol, and violently stirring for 1 hour to completely dissolve the bismuth nitrate;
(2) Transferring the mixed solution obtained in the step (1) into a polytetrafluoroethylene lining reaction kettle with the capacity of 100ml, and carrying out solvothermal reaction under the reaction conditions of 180 ℃ for 8 hours;
(3) After the reaction kettle is naturally cooled to room temperature, the bismuth oxide beta-Bi is obtained after centrifugation, washing and drying 2 O 3 。
The prepared beta-Bi 2 O 3 The photocatalytic material degrades methyl orange MO and tetracycline hydrochloride TC-HCl in water under visible light to measure the photocatalytic activity of the material, and the degradation rate of MO within 2h is found to be 40%, and the degradation rate of TC-HCl is found to be 48%.
Comparative example 3
(1) 5.000g of urea and 5.000g of melamine are uniformly mixed, calcined for 2 hours at 550 ℃ in a muffle furnace and naturally cooledAfter cooling, a block g-C is obtained 3 N 4 Grinding into powder:
(2) Taking 0.500g of bismuth nitrate, adding 50ml of ethylene glycol, and violently stirring for 1 hour to completely dissolve the bismuth nitrate;
(3) Transferring the mixed solution obtained in the step (2) into a polytetrafluoroethylene lining reaction kettle with the capacity of 100ml, and carrying out solvothermal reaction under the reaction condition of 180 ℃ for 8 hours;
(4) After the reaction kettle is naturally cooled to room temperature, the beta-Bi is obtained after centrifugation, washing and drying 2 O 3 ；
(5) Weighing 0.932g of g-C in step (1) 3 N 4 0.466g of beta-Bi in step (4) 2 O 3 The mixture was uniformly ground in an agate mortar, and the Physical mixture (Physical mixture) was collected and recorded as PBC.
The prepared PBC photocatalytic material degrades methyl orange MO and tetracycline hydrochloride TC-HCl in water under visible light to measure the photocatalytic activity of the PBC photocatalytic material, and the degradation rate of MO in 2h reaches 60%, and the degradation rate of TC-HCl reaches 56%.
FIG. 4 is g-C 3 N 4 、β-Bi 2 O 3 、PBC、β-Bi 2 O 3 /g-C 3 N 4 、β-Bi 2 O 3 /g-C 3 N 4 -1、β-Bi 2 O 3 /g-C 3 N 4 -2 photo-catalytic degradation profile of photo-catalytic material to methyl orange MO under visible light. As shown in fig. 4, when no photocatalyst was added, MO was not degraded under irradiation of visible light, indicating that MO was stable and not subjected to photolysis. Stirring in dark for 60min, establishing adsorption-desorption balance of mixed suspension, and irradiating with light source for 120min to obtain beta-Bi 2 O 3 /g-C 3 N 4 The composite material has an MO degradation efficiency of 99 percent, and g-C 3 N 4 、β-Bi 2 O 3 、PM-BC、β-Bi 2 O 3 /g-C 3 N 4 -1、β-Bi 2 O 3 /g-C 3 N 4 The degradation efficiencies of-2 were 45%, 40%, 60%, 83%, 89%, respectively.
FIG. 5 is g-C 3 N 4 、β-Bi 2 O 3 、PBC、β-Bi 2 O 3 /g-C 3 N 4 、β-Bi 2 O 3 /g-C 3 N 4 -1、β-Bi 2 O 3 /g-C 3 N 4 -2 photo-catalytic degradation diagram of the photo-catalytic material to tetracycline hydrochloride TC-HCl under visible light. As shown in FIG. 5, when no photocatalyst was added, TC-HCl was not degraded under irradiation of visible light, indicating that TC-HCl was stable and not subjected to photolysis. After the light source is started to irradiate for 150min, beta-Bi 2 O 3 /g-C 3 N 4 The degradation efficiency of the nano composite photocatalyst on TC-HCl reaches 93 percent, and g-C 3 N 4 、β-Bi 2 O 3 、PM-BC、β-Bi 2 O 3 /g-C 3 N 4 -1、β-Bi 2 O 3 /g-C 3 N 4 The degradation efficiency of-2 to TC-HCl is 34%, 48%, 56%, 85% and 81% respectively. In a solvothermal reaction, beta-Bi 2 O 3 In g-C 3 N 4 The surface grows in situ, and the two are tightly combined together. The beta-Bi in the nano composite photocatalyst can be regulated and controlled by controlling the adding amount of bismuth nitrate 2 O 3 And g-C 3 N 4 The ratio of (2) and the improvement of the photocatalysis effect are superior to those of a composite material formed by mixing a single material and physical grinding.
In the invention, under the irradiation of visible light, beta-Bi 2 O 3 And g-C 3 N 4 The photocatalysts are excited to generate electrons and holes on the respective conduction band CB and valence band VB. Due to beta-Bi 2 O 3 The conduction band potential of 0.25eV 3 N 4 Has a valence band potential of 1.50eV, and is relatively close to each other, so that beta-Bi 2 O 3 And g-C 3 N 4 Will form a direct Z-type heterojunction between the two, beta-Bi 2 O 3 Electrons in the conduction band will take precedence over g-C 3 N 4 The recombination of holes in the valence band greatly promotes the carrier separation efficiency, while leaving beta-Bi 2 O 3 Hole sum g-C in valence band 3 N 4 Electrons in the conduction band, these holes and electrons have better redox ability. Thus, electrons are leftAnd the holes react with oxygen and hydroxyl radicals adsorbed on the surface of the material respectively to generate superoxide radicals and hydroxyl radicals. Finally, these highly reactive radicals react with organic contaminants to form water and carbon dioxide.
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (3)

1. In-situ growth preparation of beta-Bi 2 O 3 /g-C 3 N 4 The method for preparing the nano composite photocatalyst is characterized by comprising the following steps of:
(1) Uniformly mixing 10g of urea and melamine according to the mass ratio of 1:1-1:4, calcining for 2h at 550 ℃ in a muffle furnace, and naturally cooling to obtain blocky g-C 3 N 4 Grinding into powder for later use;
(2) Adding 50ml of ethylene glycol into 0.2500g-1.000g of bismuth nitrate, and violently stirring for 1h to completely dissolve the bismuth nitrate;
(3) Weighing the g-C prepared in 0.9320g (1) 3 N 4 Adding into the mixture obtained in the step (2), stirring vigorously for 1h, and carrying out ultrasonic treatment for 30min;
(4) Transferring the mixed solution obtained in the step (3) into a polytetrafluoroethylene lining reaction kettle with the capacity of 100ml, and carrying out solvothermal reaction at the temperature of 160-200 ℃ for 8 hours;
(5) After the reaction kettle is naturally cooled to room temperature, the beta-Bi is obtained after centrifugation, washing and drying 2 O 3 /g-C 3 N 4 A nanocomposite;
in the step (3), the ratio of bismuth nitrate to graphite-phase carbon nitride is 0.250g:0.932g;
g to C 3 N 4 Ultrasonically dispersing the beta-Bi in glycol solution dissolved with bismuth nitrate to obtain the beta-Bi in the nano composite material 2 O 3 And g-C 3 N 4 The mass ratio of (A) to (B) is 0.1;
the obtained beta-Bi 2 O 3 /g-C 3 N 4 The nano composite material is used for degrading methyl orange MO and tetracyclic TC-HCl hydrochloride.
2. The in-situ growth preparation of beta-Bi according to claim 1 2 O 3 /g-C 3 N 4 The method for preparing the nano composite photocatalyst is characterized by comprising the following steps: the bismuth nitrate in the step (2) is Bi (NO) 3 ) 3 ·5H 2 O。
3. The in situ growth preparation of beta-Bi according to claim 1 2 O 3 /g-C 3 N 4 The method for preparing the nano composite photocatalyst is characterized by comprising the following steps: adding g-C into a solvothermal system 3 N 4 Post, beta-Bi 2 O 3 Uniformly grow in g-C 3 N 4 A surface.
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