CN111437809A - Preparation method and application of rare earth element doped bismuth silicate photocatalyst - Google Patents
Preparation method and application of rare earth element doped bismuth silicate photocatalyst Download PDFInfo
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- CN111437809A CN111437809A CN202010353643.XA CN202010353643A CN111437809A CN 111437809 A CN111437809 A CN 111437809A CN 202010353643 A CN202010353643 A CN 202010353643A CN 111437809 A CN111437809 A CN 111437809A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 40
- DQUIAMCJEJUUJC-UHFFFAOYSA-N dibismuth;dioxido(oxo)silane Chemical compound [Bi+3].[Bi+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O DQUIAMCJEJUUJC-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 44
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229960000892 attapulgite Drugs 0.000 claims abstract description 23
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 15
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 15
- -1 rare earth nitrate Chemical class 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 9
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- 238000013032 photocatalytic reaction Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 3
- 230000004298 light response Effects 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 229910052604 silicate mineral Inorganic materials 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007540 photo-reduction reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention belongs to the technical field of silicate photocatalysis, and particularly relates to a preparation method and application of a rare earth element doped bismuth silicate photocatalyst. Firstly, calcining attapulgite and ammonium sulfate in a muffle furnace, treating the calcined product with hydrochloric acid solution, centrifugally drying to obtain silicon dioxide, dissolving the silicon dioxide with tetramethyl ammonium hydroxide solution, adding bismuth nitrate and rare earth nitrate, carrying out hydrothermal reaction, centrifuging, and drying to obtain rare earth element doped bismuth silicate. The invention not only reforms the natural silicate mineral into the silicate material with visible light response, but also up-converts near infrared light into visible light through the up-conversion luminescence effect of rare earth elements, indirectly improves the sunlight utilization rate of the bismuth silicate material, and further improves the photocatalysis efficiency of the material.
Description
Technical Field
The invention belongs to the technical field of silicate photocatalysis, and particularly relates to a preparation method of a rare earth element doped bismuth silicate photocatalyst and application of the rare earth element doped bismuth silicate photocatalyst in photoreduction of carbon dioxide.
Background
Carbon dioxide (CO)2) Is a major product of fossil fuel combustion and is one of the major greenhouse gases. With the continuous change of global temperature, fossil fuels are also continuously reduced. If carbon dioxide can be converted into hydrocarbon fuel, not only can the environmental problem be solved, but also new energy can be developed. The reaction process of the photocatalysis technology is rapid and efficient, has low energy consumption, no secondary pollution, higher development value and wide application, and becomes CO2One active direction of research in processing technology.
Photocatalytic pair of CO2The resource utilization is to utilize CO2Conversion into various energy molecules (CO, CH)3OH、CH4HCOOH, etc.), has important significance for resource recycling and environmental protection. However, for reducing CO2The photocatalytic material generally has the defects of low light utilization rate and utilization range, low conversion efficiency, poor practical application and the like. In the research on the reaction of reducing carbon dioxide, the development of a novel, efficient and wide-range photo-catalytic material is a core topic for realizing the photo-catalytic carbon fixation technology.
Attapulgite (ATP for short) is a natural silicate mineral material, and has the advantages of large specific surface area, good adsorbability and the like, but the natural attapulgite only has weak response to ultraviolet light, and the application of the attapulgite in the field of photocatalysis is limited.
Disclosure of Invention
The invention takes attapulgite clay, hydrochloric acid, ammonium sulfate, bismuth nitrate, tetramethyl ammonium hydroxide and rare earth nitrate as main raw materials, combines a calcining method and a microwave hydrothermal method, and utilizes silicon dioxide in the extracted attapulgite to synthesize the rare earth ion-doped bismuth silicate photocatalyst.
The rare earth element doped bismuth silicate composite photocatalytic material provided by the invention is prepared from bismuth silicate (Bi)12SiO20) And rare earth ions (RE), wherein the mole ratio of each component in the composite photocatalytic material [ Bi3+]:[RE]X is 1: x, wherein x is in the range of 0.001mol to 0.003 mol.
The invention also provides a preparation method of the rare earth element doped bismuth silicate photocatalyst, which comprises the following specific steps:
(1) weighing a certain amount of attapulgite and ammonium sulfate, placing the attapulgite and ammonium sulfate in a crucible, calcining for 1-3h at 550 ℃ in a muffle furnace, and then placing the crucible in a hydrochloric acid solution of 3 mol/L for treatment for 2-4 h;
wherein the mass ratio of the attapulgite to the ammonium sulfate is 1: 0.33-1: 3, and the hydrochloric acid solution is diluted to 3 mol/L by adopting 35% analytically pure hydrochloric acid.
(2) Adding a small amount of tetramethyl ammonium hydroxide into deionized water, adding the silicon dioxide prepared in the step (1) under vigorous stirring, and then adding a certain amount of bismuth nitrate and a certain amount of hydrated rare earth nitrate compound (RE (NO)3)3·nH2And O), then transferring the mixture into a microwave hydrothermal kettle, and carrying out hydrothermal reaction for 60-90 min at the hydrothermal temperature of 140-180 ℃ to obtain the rare earth element doped bismuth silicate.
In the experiment, 25% tetramethyl ammonium hydroxide aqueous solution is adopted as tetramethyl ammonium hydroxide, and the concentration is about 2.38 mol/L;
the adding amount of the tetramethylammonium hydroxide corresponding to the silicon dioxide is as follows: 2.6ml:0.25g, in a mass ratio of about 2.25: 1.
The mass ratio of bismuth nitrate to silicon dioxide is 8: 1.
The molar ratio of each component in the mixed solution is [ Bi3+]:[RE]X is 1: x, wherein x is in the range of 0.001mol to 0.003 mol. The rare earth element in the hydrated nitric acid rare earth compoundThe element comprises Ce3+、Pr3+、Er3+、Tm3+，Yb3+、Sm3+、La3+The general formula is marked as RE, and the hydrated nitric acid rare earth compound is RE (NO)3)3·nH2O，，Yb3+And Er3+The hydrated nitric acid rare earth compound is Yb (NO)3·5H2O and Er (NO)3·5H2O, others being RE (NO)3)3·6H2O。
The invention also provides a photocatalytic application of the rare earth ion doped bismuth silicate composite material, and the composite material catalyst is used for photocatalytic reduction of CO2And (4) preparing methanol.
The application method comprises weighing 0.01g of prepared rare earth ion-doped bismuth silicate material, dissolving in 100m L deionized water, adding into a photocatalytic reaction device, and adding CO2Introducing into a reaction device at a flow rate of 60m L/min, and introducing N2Irradiating with 300W xenon lamp as simulated light source after 50min, collecting 1m L sample every 30min, and analyzing the concentration of methanol with gas chromatograph by using sample amount of 1 μ L, vaporizing chamber and detector temperature of 250 deg.C, maintaining column temperature of 60 deg.C for 1min, and maintaining at 10 deg.C/min-100 deg.C for 1 min.
Compared with the prior art, the invention has the beneficial effects that
(1) The method adopts the natural ore attapulgite as a silicon source for synthesizing the bismuth silicate, is cheap and easy to obtain, and is simple.
(2) The invention utilizes the up-conversion luminescence of rare earth ions to convert near infrared light into visible light, thereby widening the photoresponse range of the material.
(2) The bismuth silicate synthesized by the method has considerable yield, does not contain noble metals, is environment-friendly and economical, and is beneficial to the application of the bismuth silicate in the reaction process of photocatalytic reduction of carbon dioxide.
The invention is further illustrated with reference to the following figures and examples.
Drawings
FIG. 1 shows attapulgite and silica、Bi12SiO20And 0.0015Er3+:Bi12SiO20XRD spectrum of (1);
FIG. 2 shows the 0.0015Er prepared in example 13+:Bi12SiO20TEM pictures of the scale range of 100 nm;
FIG. 3 shows Bi12SiO20And 0.0015Er3+:Bi12SiO20Ultraviolet-visible diffuse reflection absorption spectrum diagram.
Detailed Description
The best mixture ratio and the process are preferably selected as examples, the invention contents are further explained,
Example 1
(1) Firstly weighing 2g of attapulgite, 6g of ammonium sulfate in a crucible, calcining for 2h at 550 ℃ in a muffle furnace, then placing in 3 mol/L hydrochloric acid solution at 80 ℃, carrying out water bath treatment for 2h, then centrifuging, washing for multiple times to be neutral, and drying for 12h at 80 ℃ to obtain silicon dioxide;
(2) adding 2.6ml of tetramethylammonium hydroxide into 50m L of deionized water, adding 0.25g of the silica prepared in step (1) under vigorous stirring, and adding 2g of Bi (NO) after the silica is dissolved3)3·5H2O，0.0027g Er(NO)3·5H2O, transferring the solution into a microwave hydrothermal kettle, setting the microwave power to be 400W, the hydrothermal reaction time to be 90min, and the hydrothermal temperature to be 160 ℃ to obtain 0.0015Er3+:Bi12SiO20。
0.0015Er prepared for example 1 and comparative example 13+:Bi12SiO20Performing an X-ray diffraction experiment with bismuth silicate, observing the structure and morphology under a transmission electron microscope, wherein the XRD spectrogram of the bismuth silicate and attapulgite, and silica is shown in figure 1: the calcined and acid-treated attapulgite is completely converted into silicon dioxide, and the silicon dioxide is completely converted into bismuth silicate after hydrothermal reaction, so that almost no other impurities are generated.
The TEM photograph is shown in fig. 2, and it can be seen from the figure that the rare earth ion doped bismuth silicate is elliptical, has a large specific surface area, and has wrinkles on the surface, which is advantageous for light absorption.
FIG. 3 shows bismuth silicate and 0.0015Er3+:Bi12SiO20The ultraviolet-visible diffuse reflection absorption spectrogram can see that bismuth silicate is in visible light response, and the absorption edge of the material is red-shifted after rare earth ions are doped.
The invention also provides the photo-reduction of CO by the material2The application method for preparing methanol comprises weighing 0.01g of prepared bismuth silicate, dissolving in 100m L deionized water, adding into a photocatalytic reaction device, and adding CO2Introducing into a reaction device at a flow rate of 60m L/min, and introducing N2Irradiating with 300W xenon lamp as simulated light source after 50min, collecting 1m L sample every 30min, and analyzing methanol concentration with gas chromatograph by using sample amount of 1 μ L, vaporizing chamber and detector temperature of 250 deg.C, maintaining column temperature of 60 deg.C for 1min, and maintaining at 10 deg.C/min-100 deg.C for 1min, comparing with peak area of standard sample to obtain methanol concentration in sample, and measuring methanol generation rate of 0.0015Er3+:Bi12SiO20The methanol generation rate was about 6.20. mu. mol. multidot. L-1·h-1，Bi12SiO20The methanol generation rate was about 2.40. mu. mol. multidot. L-1·h-1。
Example 2
(1) Firstly weighing 2g of attapulgite, placing 2g of ammonium sulfate in a crucible, calcining for 2h at 550 ℃ in a muffle furnace, placing in a hydrochloric acid solution of 3 mol/L after calcining at 80 ℃, carrying out water bath treatment for 2h, then centrifuging, washing for multiple times to be neutral, and drying for 12h at 80 ℃ to obtain silicon dioxide;
(2) adding 2.6ml of tetramethylammonium hydroxide into 50m L of deionized water, adding 0.25g of the silica prepared in step (1) under vigorous stirring, and adding 2g of Bi (NO) after the silica is dissolved3)3·5H2O，0.0018g Er(NO)3·5H2O, transferring the solution into a microwave hydrothermal kettle, setting the microwave power to be 400W, the hydrothermal reaction time to be 60min, and obtaining 0.001Er at the hydrothermal temperature of 140 DEG C3+:Bi12SiO20Subsequent measurements were made as in example 1, with a methanol formation rate of about 5.0. mu. mol. multidot. L-1·h-1。
Example 3
(1) Firstly weighing 2g of attapulgite, 4g of ammonium sulfate in a crucible, calcining for 2h at 550 ℃ in a muffle furnace, then placing in 3 mol/L hydrochloric acid solution at 80 ℃, carrying out water bath treatment for 2h, then centrifuging, washing for multiple times to be neutral, and drying for 12h at 80 ℃ to obtain silicon dioxide;
(2) adding 2.6ml of tetramethylammonium hydroxide into 50m L of deionized water, adding 0.25g of the silica prepared in step (1) under vigorous stirring, and adding 2g of Bi (NO) after the silica is dissolved3)3·5H2O，0.0036g Er(NO)3·5H2O, transferring the solution into a microwave hydrothermal kettle, setting the microwave power to be 400W, the hydrothermal reaction time to be 70min, and the hydrothermal temperature to be 150 ℃ to obtain 0.002Er3+:Bi12SiO20The methanol production rate was about 5.3. mu. mol. multidot. L-1·h-1。
Example 4
(1) Firstly weighing 2g of attapulgite, 1g of ammonium sulfate in a crucible, calcining for 2h at 550 ℃ in a muffle furnace, then placing in 3 mol/L hydrochloric acid solution at 80 ℃, carrying out water bath treatment for 2h, then centrifuging, washing for multiple times to be neutral, and drying for 12h at 80 ℃ to obtain silicon dioxide;
(2) adding 2.6ml of tetramethylammonium hydroxide into 50m L of deionized water, adding 0.25g of the silica prepared in step (1) under vigorous stirring, and adding 2g of Bi (NO) after the silica is dissolved3)3·5H2O，0.0045g Er(NO)3·5H2O, transferring the solution into a microwave hydrothermal kettle, setting the microwave power to be 400W, the hydrothermal reaction time to be 80min, and the hydrothermal temperature to be 170 ℃ to obtain 0.0025Er3+:Bi12SiO20The methanol production rate was about 4.3. mu. mol. multidot. L-1·h-1。
Example 5
(1) Firstly weighing 3g of attapulgite, 1g of ammonium sulfate in a crucible, calcining for 2h at 550 ℃ in a muffle furnace, then placing in 3 mol/L hydrochloric acid solution at 80 ℃, carrying out water bath treatment for 2h, then centrifuging, washing for multiple times to be neutral, and drying for 12h at 80 ℃ to obtain silicon dioxide;
(2) adding 2.6ml of tetramethylammonium hydroxide into 50m L of deionized water, adding 0.25g of the silica prepared in step (1) under vigorous stirring, and adding 2g of Bi (NO) after the silica is dissolved3)3·5H2O，0.0054g Er(NO)3·5H2O, transferring the solution into a microwave hydrothermal kettle, setting the microwave power to be 400W, carrying out hydrothermal reaction for 90min, and obtaining 0.003Er at the hydrothermal temperature of 180 DEG C3+:Bi12SiO20The methanol production rate was about 4.6. mu. mol. multidot. L-1·h-1。
Comparative example 1
(1) Firstly weighing 2g of attapulgite, 6g of ammonium sulfate in a crucible, calcining for 2h at 550 ℃ in a muffle furnace, then placing in 3 mol/L hydrochloric acid solution at 80 ℃, carrying out water bath treatment for 2h, then centrifuging, washing for multiple times to be neutral, and drying for 12h at 80 ℃ to obtain silicon dioxide;
(2) adding 2.6ml of tetramethylammonium hydroxide into 50m L of deionized water, adding 0.25g of the silica prepared in step (1) under vigorous stirring, and adding 2g of Bi (NO) after the silica is dissolved3)3·5H2O, then transferring the solution into a microwave hydrothermal kettle, setting the microwave power to be 400W, carrying out hydrothermal reaction for 90min, and carrying out hydrothermal temperature to be 160 ℃ to obtain bismuth silicate, and carrying out subsequent detection as in example 1, wherein Bi is Bi12SiO20The methanol generation rate was about 2.40. mu. mol. multidot. L-1·h-1。
Comparative example 2
2.6ml of tetramethylammonium hydroxide are taken and added to 50m L of deionized water, 0.25g of commercially available silica are added with vigorous stirring, and after the silica has dissolved 2g of Bi (NO) are added3)3·5H2O，0.0027g Er(NO)3·5H2O, transferring the solution into a microwave hydrothermal kettle, setting the microwave power to be 400W, the hydrothermal reaction time to be 90min, and the hydrothermal temperature to be 160 ℃ to obtain 0.0015Er3+:Bi12SiO20Subsequent measurements as in example 1, produced methanol at a rate of about 2.0. mu. mol. multidot. L-1·h-1。
Comparative example 3
(1) Silica was prepared as in example 1;
(2) 2.6ml of the prepared NaOH solution (about 2.8 mol/L) was added to 50m L of deionized water, 0.25g of the silica prepared in step (1) was added with vigorous stirring, and after the silica had dissolved, 2g of Bi (NO) was added3)3·5H2O，0.0027g Er(NO)3·5H2O, transferring the solution into a microwave hydrothermal kettle, setting the microwave power to be 400W, the hydrothermal reaction time to be 90min, and the hydrothermal temperature to be 160 ℃ to obtain 0.0015Er3+:Bi12SiO20Subsequent measurements as in example 1 produced methanol at a rate of about 2.3. mu. mol. multidot. L-1·h-1。
Comparative example 4
(1) Silica was prepared as in example 1;
(2) adding 2.6ml of tetramethylammonium hydroxide into 50m L of deionized water, adding 0.25g of the silica prepared in step (1) under vigorous stirring, and adding 2g of Bi (NO) after the silica is dissolved3)3·5H2O，0.0027g Er(NO)3·5H2O, transferring the solution into a hydrothermal kettle, carrying out hydrothermal reaction for 90min at the hydrothermal temperature of 160 ℃ to obtain 0.0015Er3+:Bi12SiO20Subsequent measurements as in example 1 produced methanol at a rate of about 3.1. mu. mol. multidot. L-1·h-1。
Comparative example 5
(1) Silica was prepared as in example 1;
(2) adding 1.6ml of tetramethylammonium hydroxide into 50m L of deionized water, adding 0.25g of the silica prepared in step (1) under vigorous stirring, and after the silica is dissolved, adding 2g of Bi (NO)3)3·5H2O，0.0027g Er(NO)3·5H2O, transferring the solution into a hydrothermal kettle, setting the microwave power to be 400W, the hydrothermal reaction time to be 90min, and the hydrothermal temperature to be 160 ℃ to obtain 0.0015Er3+:Bi12SiO20Subsequent measurements as in example 1, produced methanol at a rate of about 1.2. mu. mol. multidot. L-1·h-1。
Comparative example 6
(1) Silica was prepared as in example 1;
(2) adding 2.6ml of tetramethylammonium hydroxide into 50m L of deionized water, adding 0.25g of the silica prepared in step (1) under vigorous stirring, and adding 2g of Bi (NO) after the silica is dissolved3)3·5H2O，0.0072g Er(NO)3·5H2O, transferring the solution into a hydrothermal kettle, setting the microwave power to be 400W, the hydrothermal reaction time to be 90min, and the hydrothermal temperature to be 160 ℃ to obtain 0.004Er3+:Bi12SiO20Subsequent measurements as in example 1 produced methanol at a rate of about 1.6. mu. mol. multidot. L-1·h-1. It is presumed that excessive concentration of rare earth ions causes concentration quenching, which reduces the photocatalytic efficiency of the material.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (9)
1. A preparation method of a rare earth element doped bismuth silicate photocatalyst is characterized by comprising the following steps:
(1) weighing attapulgite and ammonium sulfate, placing the attapulgite and ammonium sulfate in a crucible, calcining for 1-3h at 550 ℃ in a muffle furnace, and then placing the calcined attapulgite and ammonium sulfate in 3 mol/L hydrochloric acid solution for treatment for 2-4 h;
(2) adding tetramethylammonium hydroxide into deionized water, adding the silicon dioxide prepared in the step (1) under vigorous stirring, and then adding bismuth nitrate and a hydrated rare earth nitrate compound (RE (NO)3)3·nH2O), and then transferring the mixture to a microwave hydrothermal kettle for hydrothermal reaction to obtain the rare earth element doped bismuth silicate.
2. The preparation method of the rare earth element doped bismuth silicate photocatalyst according to claim 1, wherein the mass ratio of the attapulgite to the ammonium sulfate in the step (1) is 1: 0.33-1: 3, and the hydrochloric acid solution is diluted to 3 mol/L by adopting 35% analytically pure hydrochloric acid.
3. The method of claim 1, wherein the tetramethylammonium hydroxide in step (2) is added to deionized water to form a 25% aqueous solution of tetramethylammonium hydroxide.
4. The method for preparing a rare earth element-doped bismuth silicate photocatalyst according to claim 1, wherein the rare earth element in the hydrated rare earth nitrate compound of the step (2) comprises Ce3+、Pr3+、Er3+、Tm3+，Yb3+、Sm3+、La3+。
5. The method for preparing a rare earth element-doped bismuth silicate photocatalyst according to claim 1, wherein the mass ratio of bismuth nitrate to silica in the step (2) is 8: 1.
6. The preparation method of the rare earth element doped bismuth silicate photocatalyst according to claim 1, wherein the hydrothermal reaction time in the step (2) is 60-90 min, and the hydrothermal temperature is 140-180 ℃.
7. A rare earth doped bismuth silicate photocatalyst prepared according to the method of claims 1 to 6, wherein the photocatalyst is prepared from bismuth silicate (Bi)12SiO20) And rare earth ions (RE), wherein [ Bi ] is present in the photocatalyst in a molar ratio3+]:[RE]X is 1: x, wherein x is in the range of 0.001 to 0.003 mol.
8. Use of a rare earth element doped bismuth silicate photocatalyst prepared according to the method of claims 1 to 6, characterized in that: the rare earth element doped bismuth silicate photocatalyst is used for photocatalytic reduction of CO2And (4) preparing methanol.
9. Use of a rare earth element doped bismuth silicate photocatalyst according to claim 8, characterized in that: the application method comprises the following steps: weighing the prepared rare earth ions0.01g of the sub-doped bismuth silicate material is dissolved in 100m L deionized water and then added into a photocatalytic reaction device, CO2Introducing into a reaction device at a flow rate of 60m L/min, and introducing N2Irradiating with 300W xenon lamp as simulated light source after 50min, collecting 1m L sample every 30min, and analyzing the concentration of methanol with gas chromatograph by using sample amount of 1 μ L, vaporizing chamber and detector temperature of 250 deg.C, maintaining column temperature of 60 deg.C for 1min, maintaining at 10 deg.C/min-100 deg.C for 1min, and comparing with the peak area of standard sample to determine the concentration of methanol in the sample.
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| CN113479897B (en) * | 2021-07-16 | 2023-10-24 | 常州大学 | Method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof |
| CN113479896B (en) * | 2021-07-16 | 2023-11-14 | 常州大学 | Method for preparing calcium copper silicate material by using attapulgite and biomass and application of calcium copper silicate material |
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