CN111715267A - Carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst and preparation method and application thereof - Google Patents
Carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst and preparation method and application thereof 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 50
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 42
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 24
- 229940073609 bismuth oxychloride Drugs 0.000 title claims abstract description 23
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 23
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 229910003091 WCl6 Inorganic materials 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 17
- 230000031700 light absorption Effects 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000010893 electron trap Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 238000004435 EPR spectroscopy Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
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- 238000003915 air pollution Methods 0.000 description 2
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- 239000006228 supernatant Substances 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical compound [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01D53/8625—Nitrogen oxides
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Abstract
The invention relates to a carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst and a preparation method and application thereof, wherein the method comprises the step 1 of adding g-C containing nitrogen vacancy3N4‑xPowder, WCl6Powder and NaBiO3Dispersing the powder in absolute ethyl alcohol, carrying out in-situ hydrothermal reaction on the precursor solution, wherein the reaction system is anoxic, a reduced reaction atmosphere is formed, oxygen vacancies are formed in the BiOCl, and meanwhile, WO with non-stoichiometric ratio of the oxygen vacancies is generated2.92And g-C3N4‑xIntermediate nitrogen vacancy electron trapping promotion WO3Reduction to non-stoichiometric WO2.92(ii) a Step 2, washing and drying the precipitate in the reaction solution to obtain the carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst, and irradiating the photocatalyst by visible lightCan realize the deep oxidation of the photocatalytic NO and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of photocatalyst material preparation, and particularly relates to a carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst as well as a preparation method and application thereof.
Background
The rapid development of the industry causes the air pollution to be more serious, and the sustainable development of the human society and the physical health of people are seriously influenced. The photocatalysis technology can be used for treating air pollution, has good effect, takes sunlight as a driving force, has low cost and has obvious advantages.
Photocatalytic NO removal, toxic NO during reaction2Gas and HNO2Is a main intermediate product and can generate secondary pollution. Therefore, there is a need to increase NO to the final product HNO3And (4) conversion rate. In addition, the non-activated NO molecules are difficult to adsorb and activate on the surface of the well-crystallized photocatalyst powder, which is disadvantageous for the removal of NO at ppb level.
Disclosure of Invention
The invention aims to provide a carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst, a preparation method and application thereof, the operation is simple, and the prepared g-C is3N4-x/BiOCl/WO2.92The heterojunction photocatalyst contains a large number of nitrogen vacancies and oxygen vacancies, and can realize the deep oxidation of NO under the irradiation of visible light.
In order to achieve the above purpose, the preparation method of the invention comprises the following steps:
a preparation method of a carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst comprises the following steps:
and 2, washing and drying the precipitate in the reaction solution to obtain the carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst.
Preferably, g-C containing nitrogen vacancies in step 13N4-xPowder and WCl6The mass ratio of the powder is (0.50-1.33): 1.
preferably, step 1 begins with g-C containing nitrogen vacancies3N4-xPowder and WCl6Dispersing the powder into absolute ethyl alcohol, sequentially stirring and ultrasonically treating to obtain blue turbid liquid, and finally stirring while adding NaBiO3The powder is dispersed in blue suspension and stirred to obtain the precursor solution.
Preferably, the filling ratio of the hydrothermal reaction in the step 1 is 65-80%.
Preferably, the hydrothermal reaction described in step 1 is carried out at 140 ℃ and 180 ℃.
Further, the hydrothermal reaction in step 1 is carried out at said temperature for 10-18 h.
A carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst is prepared by the preparation method of any one of the carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst.
Further, g-C3N4-xIn the nitrogen-containing vacancy, BiOCl and WO2.92Containing oxygen vacancies, which has light absorption characteristics in the visible and near infrared light range.
The application of the carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst in NO removal.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to a preparation method of a carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst, which uses g-C containing nitrogen vacancy3N4-x、WCl6And NaBiO3Dispersing the raw materials in absolute ethyl alcohol, adopting an in-situ hydrothermal growth method, and leading a reaction system to lack oxygen to formReduced reaction atmosphere, resulting in the formation of oxygen vacancies in the BiOCl, with the formation of non-stoichiometric WO containing oxygen vacancies2.92And g-C3N4-xIntermediate nitrogen vacancy electron trapping promotion WO3Reduction to non-stoichiometric WO2.92g-C containing double defects is prepared3N4-x/BiOCl/WO2.92The heterojunction photocatalyst can realize photocatalytic NO deep oxidation under the irradiation of visible light, and has good application prospect. The defects are introduced into the catalyst powder, so that the adsorption and activation capability of the catalyst powder on NO molecules can be improved, and the light absorption characteristic of the photocatalyst can be improved, so that the photocatalytic activity is improved.
g-C of the invention3N4-x/BiOCl/WO2.92The heterojunction photocatalyst enhances light absorption due to the presence of nitrogen and oxygen vacancies, while the LSPR effect of the oxygen vacancies causes g-C3N4-x/BiOCl/WO2.92The light absorption of the heterojunction photocatalyst in the visible-near infrared light range is obviously enhanced, and the main oxidation product during the photocatalytic NO removal is HNO3Only trace amounts of HNO are produced2And NO toxic NO is generated2Gas, has good application prospect.
Drawings
FIG. 1 is an XRD pattern of a catalyst powder prepared according to the present invention, wherein a to c are XRD patterns of powders prepared in examples 1 to 3, respectively.
FIG. 2 is an EPR chart of a catalyst powder prepared by the present invention, and b is an EPR chart of a powder prepared in example 2.
FIG. 3 is a diagram of UV-vis-NIR DRS of catalyst powder prepared according to the present invention, wherein a-c are diagrams of UV-vis-NIR DRS of powder prepared according to examples 1-3, respectively.
FIG. 4 is a graph showing the NO removal curves of the catalyst powder prepared according to the present invention under irradiation of visible light, wherein a-c are the NO removal curves of the powders prepared in examples 1-3, respectively.
FIG. 5 shows the real-time NO and NO during the NO removal process under visible light irradiation of the catalyst powder prepared by the present invention2The concentrations of the powders prepared in examples 1 to 3 are shown in the graphs as a to cNO and NO during catalytic NO removal2The real-time concentration of (c).
FIG. 6 shows NO in the supernatant after photocatalytic NO removal, ultrasonic washing with deionized water, and filtration of the powder prepared in example 22 -And NO3 -The concentration of the ions.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings.
The invention relates to a preparation method of a carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst, which comprises the following steps:
step 1: placing 30g of urea in a quartz crucible with a cover, placing the crucible in a muffle furnace, heating from room temperature to 550 ℃ at a heating rate of 15 ℃/min, preserving heat for 4h, cooling to 50 ℃ along with the furnace to obtain g-C containing nitrogen vacancy3N4-xPowder;
step 2: a certain amount of g-C3N4-xAnd WCl6Dispersing the powder into 40mL of absolute ethyl alcohol, stirring for 30min, and carrying out ultrasonic treatment for 60min to obtain blue suspension;
and step 3: while magnetically stirring, adding a certain amount of NaBiO3Dispersing the powder into the suspension, stirring for 30min to obtain light brown suspension, i.e. reaction precursor solution, wherein the molar ratio of Bi element to Cl element in the reaction precursor solution is (0.15-0.5): 1;
and 4, step 4: the reaction precursor solution is placed in a hydrothermal reaction kettle, the reaction filling ratio is 65-80%, the temperature is increased from room temperature to 140-180 ℃ within 60min, the reaction is finished after the temperature is kept for 10-18h, the reaction time is short, and the reaction condition is mild.
And 5: after the reaction is finished, naturally cooling to room temperature, washing the obtained precipitate for 3 times by deionized water and absolute ethyl alcohol respectively, and drying at the constant temperature of 70 ℃ for 12 hours to obtain g-C3N4-x/BiOCl/WO2.92A heterojunction photocatalyst.
Wherein g-C3N4-xNitrogen-containing vacancies in the middle; BiOCl and non-stoichiometric ratio WO2.92In which oxygen vacancies are formed, the reaction atmosphere of the reduction necessarily causes the formation of oxygen vacancies in the BiOCl；WO2.92Tungsten oxide in non-stoichiometric proportions, with WO in stoichiometric proportions3Correspondingly, exhibiting enhanced light absorption properties in the visible and near infrared range, the main product during photocatalytic NO removal is HNO3Only trace amounts of HNO are produced2And NO toxic NO is generated2A gas.
Example 1:
step 1: placing 30g of urea in a quartz crucible with a cover, placing the crucible in a muffle furnace, heating from room temperature to 550 ℃ at a heating rate of 15 ℃/min, preserving heat for 4h, cooling to 50 ℃ along with the furnace to obtain g-C containing nitrogen vacancy3N4-xPowder;
step 2: 0.3g of g-C3N4-xAnd 0.225g of WCl6Dispersing the powder into 40mL of absolute ethyl alcohol, stirring for 30min, and carrying out ultrasonic treatment for 60min to obtain blue suspension;
and step 3: while magnetically stirring, 0.238g of NaBiO was added3Dispersing the powder into the suspension, wherein the molar ratio of Bi element to Cl element is 0.25:1, and stirring for 30min to obtain light brown suspension, namely reaction precursor liquid;
and 4, step 4: and (3) placing the reaction precursor solution into a hydrothermal reaction kettle, wherein the reaction filling ratio is about 65%, heating the reaction kettle to 140 ℃ from room temperature after 60min, and preserving the heat for 14h to finish the reaction.
And 5: after the reaction is finished, naturally cooling to room temperature, washing the obtained precipitate for 3 times by deionized water and absolute ethyl alcohol respectively, and drying at the constant temperature of 70 ℃ for 12 hours to obtain g-C3N4-x/BiOCl/WO2.92A heterojunction photocatalyst.
Example 2:
step 1: placing 30g of urea in a quartz crucible with a cover, placing the crucible in a muffle furnace, heating from room temperature to 550 ℃ at a heating rate of 15 ℃/min, preserving heat for 4h, cooling to 50 ℃ along with the furnace to obtain g-C containing nitrogen vacancy3N4-xPowder;
step 2: 0.3g of g-C3N4-xAnd 0.225g of WCl6Dispersing the powder into 40mL of absolute ethyl alcohol, stirring for 30min,Carrying out ultrasonic treatment for 60min to obtain blue suspension;
and step 3: while magnetically stirring, 0.476g of NaBiO was added3Dispersing the powder into the suspension, wherein the molar ratio of Bi element to Cl element is 0.5:1, and stirring for 30min to obtain light brown suspension, namely reaction precursor liquid;
and 4, step 4: and (3) placing the reaction precursor solution into a hydrothermal reaction kettle, wherein the reaction filling ratio is about 80%, heating the reaction kettle to 160 ℃ from room temperature for 60min, and preserving the heat for 16h to finish the reaction.
And 5: after the reaction is finished, naturally cooling to room temperature, washing the obtained precipitate for 3 times by deionized water and absolute ethyl alcohol respectively, and drying at the constant temperature of 70 ℃ for 12 hours to obtain g-C3N4-x/BiOCl/WO2.92A heterojunction photocatalyst.
Example 3:
step 1: placing 30g of urea in a quartz crucible with a cover, placing the crucible in a muffle furnace, heating from room temperature to 550 ℃ at a heating rate of 15 ℃/min, preserving heat for 4h, cooling to 50 ℃ along with the furnace to obtain g-C containing nitrogen vacancy3N4-xPowder;
step 2: 0.3g of g-C3N4-xAnd 0.60g of WCl6Dispersing the powder into 40mL of absolute ethyl alcohol, stirring for 30min, and carrying out ultrasonic treatment for 60min to obtain blue suspension;
and step 3: while magnetically stirring, 0.476g of NaBiO was added3Dispersing the powder into the suspension, wherein the molar ratio of Bi element to Cl element is 0.19:1, and stirring for 30min to obtain light brown suspension, namely reaction precursor liquid;
and 4, step 4: and (3) placing the reaction precursor solution into a hydrothermal reaction kettle, wherein the reaction filling ratio is about 75%, heating the reaction kettle to 180 ℃ from room temperature for 60min, and preserving the temperature for 18h to finish the reaction.
And 5: after the reaction is finished, naturally cooling to room temperature, washing the obtained precipitate for 3 times by deionized water and absolute ethyl alcohol respectively, and drying at the constant temperature of 70 ℃ for 12 hours to obtain g-C3N4-x/BiOCl/WO2.92A heterojunction photocatalyst.
Example 4:
step 1: placing 30g of urea in a quartz crucible with a cover, placing the crucible in a muffle furnace, heating from room temperature to 550 ℃ at a heating rate of 15 ℃/min, preserving heat for 4h, cooling to 50 ℃ along with the furnace to obtain g-C containing nitrogen vacancy3N4-xPowder;
step 2: 0.6g of g-C3N4-xAnd 0.60g of WCl6Dispersing the powder into 40mL of absolute ethyl alcohol, stirring for 30min, and carrying out ultrasonic treatment for 60min to obtain blue suspension;
and step 3: while magnetically stirring, 0.376g of NaBiO was added3Dispersing the powder into the suspension, wherein the molar ratio of Bi element to Cl element is 0.15:1, and stirring for 30min to obtain light brown suspension, namely reaction precursor liquid;
and 4, step 4: and (3) placing the reaction precursor solution into a hydrothermal reaction kettle, wherein the reaction filling ratio is about 70%, heating the reaction kettle to 170 ℃ from room temperature for 60min, and preserving the temperature for 10h to finish the reaction.
And 5: after the reaction is finished, naturally cooling to room temperature, washing the obtained precipitate for 3 times by deionized water and absolute ethyl alcohol respectively, and drying at the constant temperature of 70 ℃ for 12 hours to obtain g-C3N4-x/BiOCl/WO2.92A heterojunction photocatalyst.
FIG. 1 is an XRD pattern of the powder, wherein a to c are XRD patterns of the powders prepared in examples 1 to 3, respectively. In XRD patterns of the powders prepared in examples 1 to 3, g to C were observed3N4-xBiOCl and WO2.92The coexistence of three phases in the sample is proved. Wherein BiOCl belongs to a tetragonal system, and the space point group is P4/nmm; WO2.92Belonging to the monoclinic system, the space point group is P2/c.
FIG. 2 is an EPR chart of the powder. In the figure, b is an EPR chart of the powder prepared in example 2. g-C3N4-xAnd BiOCl/WO2.92The weak EPR signal is due to the presence of nitrogen and oxygen vacancies, respectively. The nitrogen vacancy and the oxygen vacancy are both positive centers and capture electrons to balance the charge of the system; the defect site single electron paramagnetic resonance phenomenon results in the generation of an EPR signal. g-C3N4-x/BiOCl/WO2.92EPR signaling of heterojunction photocatalystsIs significantly stronger than g-C3N4-xAnd BiOCl/WO2.92An increased defect concentration is demonstrated. The hydrothermal reaction with absolute ethyl alcohol as reaction medium has oxygen deficiency to form reducing reaction atmosphere, so that oxygen vacancy is formed in BiOCl, and WO with oxygen vacancy in non-stoichiometric ratio is generated2.92And g-C3N4-xIntermediate nitrogen vacancy electron trapping promotion WO3Reduction to non-stoichiometric WO2.92。
FIG. 3 is a diagram of UV-vis-NIR DRS of catalyst powder prepared according to the present invention. In the figure, a-c are UV-vis-NIR DRS diagrams of the powder prepared in examples 1-3 respectively. The g-C is caused by the fact that nitrogen and oxygen vacancies can form defect states, i.e., donor levels, between the forbidden bands of the semiconductor3N4-x/BiOCl/WO2.92The UV-vis-NIR DRS diagram of the heterojunction photocatalyst shows obvious light absorption shoulders near the absorption edge, and the LSPR effect of the oxygen vacancy leads g-C3N4-x/BiOCl/WO2.92The light absorption of the heterojunction photocatalyst in the visible-near infrared light range is obviously enhanced.
FIG. 4 is a graph showing the NO removal curves of the catalyst powder prepared according to the present invention under irradiation of visible light, wherein a-c are the NO removal curves of the powders prepared in examples 1-3, respectively. C/C of ordinate in FIG. 40Is the ratio of the concentration of NO after degradation to its initial concentration. As seen from the figure, g-C prepared3N4-x/BiOCl/WO2.92The heterojunction photocatalyst shows a significant increase over g-C3N4-xAnd BiOCl/WO2.92Photocatalytic Properties of (1), examples 1 to 33N4-x/BiOCl/WO2.92After the heterojunction photocatalyst is irradiated by visible light for 10min, the NO removal rate can reach 58.24%, 68.70% and 64.27%.
FIG. 5 shows the real-time NO and NO during the NO removal process under visible light irradiation of the catalyst powder prepared by the present invention2Concentrations, a-c in the graph are NO and NO during photocatalytic NO removal of the powders prepared in examples 1-3, respectively2The real-time concentration of (c). As can be seen from the graph, NO is gradually decreased with the concentration of NO during the photocatalytic reaction2Is rich inThe degree is not obviously increased and even shows a gradually reduced trend, and the prepared g-C is proved3N4-x/BiOCl/WO2.92The heterojunction photocatalyst does not generate toxic intermediate NO during the photocatalytic NO removal2Even the original NO in the system can be converted into2And (5) removing.
FIG. 6 shows NO in the supernatant after photocatalytic NO removal, ultrasonic washing with deionized water, and filtration of the powder prepared in example 22 -And NO3 -The concentration of the ions. NO2 -The ion concentration is only 1.303g/L, and NO3 -The ion concentration is as high as 41.442g/L, which proves that the prepared g-C3N4-x/BiOCl/WO2.92The main product of the heterojunction photocatalyst during photocatalytic NO removal is HNO3Only trace amounts of HNO are produced2。
Claims (9)
1. A preparation method of a carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst is characterized by comprising the following steps:
step 1, adding g-C containing nitrogen vacancy3N4-xPowder, WCl6Powder and NaBiO3Dispersing the powder in absolute ethyl alcohol to obtain a precursor solution, and carrying out hydrothermal reaction on the precursor solution, wherein the molar ratio of Bi element to Cl element in the precursor solution is (0.15-0.5):1 to obtain a reaction solution;
and 2, washing and drying the precipitate in the reaction solution to obtain the carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst.
2. The method for preparing a carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst as claimed in claim 1, wherein g-C containing nitrogen vacancies in step 13N4-xPowder and WCl6The mass ratio of the powder is (0.50-1.33): 1.
3. the method for preparing a carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst as claimed in claim 1, wherein the nitrogen-containing vacancy is firstly generated in step 1g-C3N4-xPowder and WCl6Dispersing the powder into absolute ethyl alcohol, sequentially stirring and ultrasonically treating to obtain blue turbid liquid, and finally stirring while adding NaBiO3The powder is dispersed in blue suspension and stirred to obtain the precursor solution.
4. The method for preparing a carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst as claimed in claim 1, wherein the filling ratio of the hydrothermal reaction in the step 1 is 65-80%.
5. The method as claimed in claim 1, wherein the hydrothermal reaction in step 1 is carried out at 140-180 ℃.
6. The method for preparing a carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst as claimed in claim 5, wherein the hydrothermal reaction in the step 1 is carried out at the temperature for 10-18 h.
7. A carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst, which is characterized by being obtained by the preparation method of the carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst according to any one of claims 1 to 6.
8. The carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst of claim 7 wherein g-C3N4-xIn the nitrogen-containing vacancy, BiOCl and WO2.92Containing oxygen vacancies, which has light absorption characteristics in the visible and near infrared light range.
9. Use of a carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst as claimed in claim 8 for the removal of NO.
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