CN111437809B - 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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- CN111437809B CN111437809B CN202010353643.XA CN202010353643A CN111437809B CN 111437809 B CN111437809 B CN 111437809B CN 202010353643 A CN202010353643 A CN 202010353643A CN 111437809 B CN111437809 B CN 111437809B
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 35
- 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 34
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 43
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 40
- 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 26
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 26
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 18
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- -1 rare earth nitrate Chemical class 0.000 claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- 238000007146 photocatalysis Methods 0.000 claims abstract description 7
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 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 11
- 238000005303 weighing Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000013032 photocatalytic reaction Methods 0.000 claims description 3
- 238000009834 vaporization Methods 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
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims 2
- 238000001035 drying Methods 0.000 abstract description 8
- 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 3
- 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 30
- 239000001569 carbon dioxide Substances 0.000 description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 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
- 238000006722 reduction reaction Methods 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum 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
- 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
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 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
- 239000000203 mixture 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
- 238000007540 photo-reduction reaction Methods 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
Classifications
-
- 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
- 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
-
- B01J35/39—
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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, then dissolving the silicon dioxide by adopting tetramethylammonium hydroxide solution, adding bismuth nitrate and rare earth nitrate, and centrifugally drying after hydrothermal reaction to obtain the rare earth element doped bismuth silicate. According to the invention, natural silicate minerals are transformed into silicate materials with visible light response, near infrared light is up-converted into visible light through up-conversion luminescence effect of rare earth elements, and sunlight utilization rate of bismuth silicate materials is indirectly improved, so that photocatalysis efficiency of the materials is improved.
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 photo-reduced 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 ever changing global air temperature, fossil fuels are also continually decreasing. If the carbon dioxide can be converted into hydrocarbon fuel, not only the environmental problem can be solved, but also new energy sources can be developed. The reaction process of the photocatalysis technology is quick and efficient, has low energy consumption and no secondary pollution, has higher development value and wide application, and becomes CO 2 One direction of active research in processing technology.
Photocatalytic CO 2 The resource utilization is to make CO 2 Is converted into various energy molecules (CO, CH 3 OH、CH 4 HCOOH, etc.), and has important significance for resource recycling and environmental protection. However, for reduction of CO 2 The 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 reaction research of reducing carbon dioxide at present, the development of novel, efficient and wide-photoresponsive photocatalytic materials is a core subject for realizing the photocatalytic carbon fixation technology.
Attapulgite (ATP for short) is a natural silicate mineral material and has the advantages of large specific surface area, good adsorptivity and the like, but the natural attapulgite has weak response to ultraviolet light, so that the application of the attapulgite in the field of photocatalysis is limited.
Disclosure of Invention
The invention uses attapulgite clay, hydrochloric acid, ammonium sulfate, bismuth nitrate, tetramethyl ammonium hydroxide and rare earth nitrate as main raw materials, combines a calcination method and a microwave hydrothermal method, and synthesizes the rare earth ion doped bismuth silicate photocatalyst by utilizing silicon dioxide in the extracted attapulgite.
The rare earth element doped bismuth silicate composite photocatalytic material provided by the invention is prepared from bismuth silicate (Bi 12 SiO 20 ) And rare earth ions (RE), wherein the molar ratio of each component [ Bi ] in the composite photocatalytic material 3+ ]:[RE]X is in the range of 0.001mol to 0.003mol.
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 the attapulgite and ammonium sulfate in a muffle furnace at 550 ℃ for 1-3h, and then placing the attapulgite and ammonium sulfate in a hydrochloric acid solution with the concentration of 3mol/L for 2-4h;
wherein the mass ratio of the attapulgite to the ammonium sulfate is 1:0.33-1:3; the hydrochloric acid solution was diluted to 3mol/L with 35% analytically pure hydrochloric acid.
(2) Adding a small amount of tetramethylammonium hydroxide to deionized water, adding the silica prepared in step (1) with vigorous stirring, and then adding a certain amount of bismuth nitrate and a hydrated rare earth nitrate compound (RE (NO) 3 ) 3 ·nH 2 O), then transferring the mixture into a microwave hydrothermal kettle, and obtaining the rare earth element doped bismuth silicate after hydrothermal reaction for 60-90 min and hydrothermal temperature of 140-180 ℃.
In the experiment, the tetramethylammonium hydroxide adopts a 25% tetramethylammonium hydroxide aqueous solution, and the concentration is about 2.38mol/L;
the amount of tetramethylammonium hydroxide added to the silica was: 2.6ml to 0.25g, mass ratio of about 2.25 to 1.
The mass ratio of bismuth nitrate to silicon dioxide is 8:1.
The molar ratio of each component in the mixed solution is [ Bi ] 3+ ]:[RE]X is in the range of 0.001mol to 0.003mol. The rare earth elements in the hydrated rare earth nitrate compound comprise Ce 3+ 、Pr 3+ 、Er 3+ 、Tm 3+ ，Yb 3+ 、Sm 3+ 、La 3+ The general formula is RE, the hydrated rare earth nitrate compound is RE (NO) 3 ) 3 ·nH 2 O，，Yb 3+ And Er 3+ Is Yb (NO) 3 ·5H 2 O and Er (NO) 3 ·5H 2 O, other is RE (NO) 3 ) 3 ·6H 2 O。
The invention also provides a photocatalysis application of the rare earth ion doped bismuth silicate composite material, and the composite material catalyst is used for photocatalytic reduction of CO 2 And (5) preparing methanol.
The application method comprises the following steps: weighing 0.01g of prepared rare earth ion doped bismuth silicate material, dissolving in 100mL of deionized water, adding into a photocatalytic reaction device, and adding CO 2 Introducing into a reaction device at a flow rate of 60mL/min, and introducing N 2 After 50min, a xenon lamp with the power of 300W is used as a simulated light source for irradiation, 1mL of sample is collected every 30min, and the concentration of methanol is analyzed by a gas chromatograph, and the testing method comprises the following steps: the sample injection amount is 1 mu L, the temperature of the vaporization chamber and the detector is 250 ℃, the column temperature is kept at 60 ℃ for 1min, and then the sample is kept at 10 ℃/min to 100 ℃ for 1min. The concentration of methanol in the sample was measured by comparison with the peak area of the standard.
Compared with the prior art, the invention has the beneficial effects that
(1) The invention adopts the natural ore attapulgite as the silicon source for synthesizing the bismuth silicate, and has low cost, easy obtainment and simple method.
(2) The invention utilizes the up-conversion luminescence of rare earth ions to convert near infrared light into visible light, and widens the light response range of the material.
(2) The bismuth silicate synthesized by the method has considerable yield, does not contain noble metal, 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 will be further described with reference to the drawings and examples.
Drawings
FIG. 1 shows attapulgite, silica, bi 12 SiO 20 0.0015Er 3+ :Bi 12 SiO 20 XRD pattern of (b);
FIG. 2 is a 0.0015Er prepared in example 1 3+ :Bi 12 SiO 20 TEM image of the scale range of 100 nm;
FIG. 3 is Bi 12 SiO 20 0.0015Er 3+ :Bi 12 SiO 20 Is a diffuse reflection absorption spectrum of ultraviolet-visible light.
Detailed Description
Examples preferred optimum proportions and technical procedures are exemplified to further illustrate the summary of the invention,
Example 1
(1) Firstly, weighing 2g of attapulgite, placing 6g of ammonium sulfate in a crucible, calcining for 2 hours at 550 ℃ in a muffle furnace, placing in a hydrochloric acid solution of 3mol/L after calcining, treating for 2 hours in a water bath at 80 ℃, centrifuging, washing for many times to be neutral, and drying for 12 hours at 80 ℃ to obtain silicon dioxide;
(2) Adding 2.6mL of tetramethylammonium hydroxide into 50mL of deionized water, adding 0.25g of the silica prepared in the step (1) under vigorous stirring, and adding 2g of Bi (NO) after the silica is dissolved 3 ) 3 ·5H 2 O，0.0027g Er(NO) 3 ·5H 2 O then transferring the solution into a microwave hydrothermal kettle, setting microwave power to 400W, and obtaining 0.0015Er at 160 ℃ after hydrothermal reaction time of 90min 3+ :Bi 12 SiO 20 。
0.0015Er prepared in comparative example 1 and comparative example 1 3+ :Bi 12 SiO 20 And carrying out an X-ray diffraction experiment on the bismuth silicate, observing the structure and the morphology of the bismuth silicate under a transmission electron microscope, wherein the XRD spectrum of the bismuth silicate, attapulgite and silicon dioxide is shown in figure 1: the attapulgite after the calcination and acid treatment is completely converted into silicon dioxide, and the silicon dioxide is completely converted into bismuth silicate after the 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 folds on the surface, which is favorable for light absorption.
FIG. 3 is bismuth silicate and 0.0015Er 3+ :Bi 12 SiO 20 Ultraviolet (V) ray-The diffuse reflection absorption spectrum is visible, and the bismuth silicate is visible light response, and the absorption edge of the material is red shifted after being doped with rare earth ions.
The invention also provides the material for photo-reduction of CO 2 The application method for preparing the methanol comprises the following steps: weighing 0.01g of prepared bismuth silicate, dissolving in 100mL of deionized water, adding into a photocatalytic reaction device, and adding CO 2 Introducing into a reaction device at a flow rate of 60mL/min, and introducing N 2 After 50min, a xenon lamp with the power of 300W is used as a simulated light source for irradiation, 1mL of sample is collected every 30min, and the concentration of methanol is analyzed by a gas chromatograph, and the testing method comprises the following steps: the sample injection amount is 1 mu L, the temperature of the vaporization chamber and the detector is 250 ℃, the column temperature is kept at 60 ℃ for 1min, and then the sample is kept at 10 ℃/min to 100 ℃ for 1min. The concentration of methanol in the sample was measured by comparison with the peak area of the standard. The methanol formation rate of the sample was measured as: 0.0015Er 3+ :Bi 12 SiO 20 The methanol production rate was about 6.20. Mu. Mol.L -1 ·h -1 ，Bi 12 SiO 20 The methanol production rate was about 2.40. Mu. Mol.L -1 ·h -1 。
Example 2
(1) Firstly, weighing 2g of attapulgite, placing 2g of ammonium sulfate in a crucible, calcining for 2 hours at 550 ℃ in a muffle furnace, placing in a hydrochloric acid solution of 3mol/L after calcining, treating for 2 hours in a water bath at 80 ℃, centrifuging, washing for many times to be neutral, and drying for 12 hours at 80 ℃ to obtain silicon dioxide;
(2) Adding 2.6mL of tetramethylammonium hydroxide into 50mL of deionized water, adding 0.25g of the silica prepared in the step (1) under vigorous stirring, and adding 2g of Bi (NO) after the silica is dissolved 3 ) 3 ·5H 2 O，0.0018g Er(NO) 3 ·5H 2 O then transferring the solution into a microwave hydrothermal kettle, setting microwave power to 400W, and obtaining 0.001Er after hydrothermal reaction time of 60min and hydrothermal temperature of 140 DEG C 3+ :Bi 12 SiO 20 Subsequent testing was performed as in example 1, with a methanol formation rate of about 5.0. Mu. Mol.L -1 ·h -1 。
Example 3
(1) Firstly, weighing 2g of attapulgite, placing 4g of ammonium sulfate in a crucible, calcining for 2 hours at 550 ℃ in a muffle furnace, placing in a hydrochloric acid solution of 3mol/L after calcining, treating for 2 hours in a water bath at 80 ℃, centrifuging, washing for many times to be neutral, and drying for 12 hours at 80 ℃ to obtain silicon dioxide;
(2) Adding 2.6mL of tetramethylammonium hydroxide into 50mL of deionized water, adding 0.25g of the silica prepared in the step (1) under vigorous stirring, and adding 2g of Bi (NO) after the silica is dissolved 3 ) 3 ·5H 2 O，0.0036g Er(NO) 3 ·5H 2 O then transferring the solution into a microwave hydrothermal kettle, setting microwave power to 400W, carrying out hydrothermal reaction for 70min, and obtaining 0.002Er at a hydrothermal temperature of 150 DEG C 3+ :Bi 12 SiO 20 The methanol production rate was about 5.3. Mu. Mol.L -1 ·h -1 。
Example 4
(1) Firstly, weighing 2g of attapulgite, placing 1g of ammonium sulfate in a crucible, calcining for 2 hours at 550 ℃ in a muffle furnace, placing in a hydrochloric acid solution of 3mol/L after calcining, treating for 2 hours in a water bath at 80 ℃, centrifuging, washing for many times to be neutral, and drying for 12 hours at 80 ℃ to obtain silicon dioxide;
(2) Adding 2.6mL of tetramethylammonium hydroxide into 50mL of deionized water, adding 0.25g of the silica prepared in the step (1) under vigorous stirring, and adding 2g of Bi (NO) after the silica is dissolved 3 ) 3 ·5H 2 O，0.0045g Er(NO) 3 ·5H 2 O then transferring the solution into a microwave hydrothermal kettle, setting microwave power to 400W, and obtaining 0.0025Er at 170 ℃ after hydrothermal reaction time of 80min 3+ :Bi 12 SiO 20 The methanol production rate was about 4.3. Mu. Mol.L -1 ·h -1 。
Example 5
(1) Firstly, weighing 3g of attapulgite, placing 1g of ammonium sulfate in a crucible, calcining for 2 hours at 550 ℃ in a muffle furnace, placing in a hydrochloric acid solution of 3mol/L after calcining, treating for 2 hours in a water bath at 80 ℃, centrifuging, washing for many times to be neutral, and drying for 12 hours at 80 ℃ to obtain silicon dioxide;
(2) 2.6mL of tetramethylammonium hydroxide was added to 50mL of deionized water, and 0.25g of the second prepared in step (1) was added with vigorous stirringSilica, after dissolving the silica, 2g Bi (NO) 3 ) 3 ·5H 2 O，0.0054g Er(NO) 3 ·5H 2 O then transferring the solution into a microwave hydrothermal kettle, setting microwave power to 400W, carrying out hydrothermal reaction for 90min, and obtaining 0.003Er at the hydrothermal temperature of 180 DEG C 3+ :Bi 12 SiO 20 The methanol production rate was about 4.6. Mu. Mol.L -1 ·h -1 。
Comparative example 1
(1) Firstly, weighing 2g of attapulgite, placing 6g of ammonium sulfate in a crucible, calcining for 2 hours at 550 ℃ in a muffle furnace, placing in a hydrochloric acid solution of 3mol/L after calcining, treating for 2 hours in a water bath at 80 ℃, centrifuging, washing for many times to be neutral, and drying for 12 hours at 80 ℃ to obtain silicon dioxide;
(2) Adding 2.6mL of tetramethylammonium hydroxide into 50mL of deionized water, adding 0.25g of the silica prepared in the step (1) under vigorous stirring, and adding 2g of Bi (NO) after the silica is dissolved 3 ) 3 ·5H 2 O, transferring the solution into a microwave hydrothermal kettle, setting microwave power to 400W, performing hydrothermal reaction for 90min, and obtaining bismuth silicate at 160 ℃ for subsequent detection as in example 1, bi 12 SiO 20 The methanol production rate was about 2.40. Mu. Mol.L -1 ·h -1 。
Comparative example 2
2.6mL of tetramethylammonium hydroxide was added to 50mL of deionized water, 0.25g of commercially available silica was added with vigorous stirring, and after dissolution of the silica, 2g of Bi (NO 3 ) 3 ·5H 2 O，0.0027g Er(NO) 3 ·5H 2 O then transferring the solution into a microwave hydrothermal kettle, setting microwave power to 400W, and obtaining 0.0015Er at 160 ℃ after hydrothermal reaction time of 90min 3+ :Bi 12 SiO 20 . Subsequent runs were performed as in example 1, with a methanol formation rate of about 2.0. Mu. Mol.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 50mL of deionized water under vigorous conditionsAdding 0.25g of the silica prepared in the step (1) under stirring, and adding 2g of Bi (NO) after the silica is dissolved 3 ) 3 ·5H 2 O，0.0027g Er(NO) 3 ·5H 2 O then transferring the solution into a microwave hydrothermal kettle, setting microwave power to 400W, and obtaining 0.0015Er at 160 ℃ after hydrothermal reaction time of 90min 3+ :Bi 12 SiO 20 . Subsequent runs were performed as in example 1, with a methanol formation rate of about 2.3. Mu. Mol.L -1 ·h -1 。
Comparative example 4
(1) Silica was prepared as in example 1;
(2) Adding 2.6mL of tetramethylammonium hydroxide into 50mL of deionized water, adding 0.25g of the silica prepared in the step (1) under vigorous stirring, and adding 2g of Bi (NO) after the silica is dissolved 3 ) 3 ·5H 2 O，0.0027g Er(NO) 3 ·5H 2 O then transferring the solution into a hydrothermal kettle, and obtaining 0.0015Er at 160 ℃ after the hydrothermal reaction time is 90min 3+ :Bi 12 SiO 20 . Subsequent runs were performed as in example 1, with a methanol formation rate of about 3.1. Mu. Mol.L -1 ·h -1 。
Comparative example 5
(1) Silica was prepared as in example 1;
(2) 1.6mL of tetramethylammonium hydroxide was added to 50mL of deionized water, 0.25g of the silica prepared in step (1) was added with vigorous stirring, and after the silica was dissolved, 2g of Bi (NO) 3 ) 3 ·5H 2 O，0.0027g Er(NO) 3 ·5H 2 O then transferring the solution into a hydrothermal kettle, setting microwave power to 400W, and obtaining 0.0015Er at 160 ℃ after hydrothermal reaction time of 90min 3+ :Bi 12 SiO 20 . Subsequent runs were performed as in example 1, with a methanol formation rate of about 1.2. Mu. Mol.L -1 ·h -1 。
Comparative example 6
(1) Silica was prepared as in example 1;
(2) 2.6mL of tetramethylammonium hydroxide was added to 50mL of deionized water, and 0.25g of the solution prepared in step (1) was added with vigorous stirringSilica, after dissolving the silica, 2g Bi (NO) 3 ) 3 ·5H 2 O，0.0072g Er(NO) 3 ·5H 2 O then transferring the solution into a hydrothermal kettle, setting microwave power to 400W, and obtaining 0.004Er after hydrothermal reaction time of 90min and hydrothermal temperature of 160 DEG C 3+ :Bi 12 SiO 20 . Subsequent runs were performed as in example 1, with a methanol formation rate of about 1.6. Mu. Mol.L -1 ·h -1 . It is presumed that too large a concentration of rare earth ions causes concentration quenching, which reduces the photocatalytic efficiency of the material.
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.
Claims (6)
1. CO reduction method for photocatalysis 2 A rare earth element doped bismuth silicate photocatalyst for preparing methanol is characterized in that the photocatalyst consists of bismuth silicate Bi 12 SiO 20 And rare earth ions RE, wherein, in the photocatalyst, the molar ratio of [ Bi ] 3+ ]:[RE]X, wherein x ranges from 0.001 to 0.003;
the preparation method of the photocatalyst comprises the following steps:
(1) Weighing attapulgite and ammonium sulfate, placing the attapulgite and the ammonium sulfate in a crucible, calcining the attapulgite and the ammonium sulfate in a muffle furnace at 550 ℃ for 1-3h, and then placing the attapulgite and the ammonium sulfate in a hydrochloric acid solution with the concentration of 3mol/L for 2-4h;
the mass ratio of the attapulgite to the ammonium sulfate is 1:0.33-1:3;
(2) Adding tetramethyl ammonium hydroxide into deionized water, adding the silicon dioxide prepared in the step (1) under intense stirring, then adding bismuth nitrate and a hydrated rare earth nitrate compound, and then transferring into a microwave hydrothermal kettle for hydrothermal reaction to obtain rare earth element doped bismuth silicate;
the mass ratio of the tetramethylammonium hydroxide to the silicon dioxide is 2.25:1;
the microwave power is 400W, the hydrothermal reaction time is 60-90 min, and the hydrothermal temperature is 140-180 ℃.
2. The rare earth doped bismuth silicate photocatalyst according to claim 1, wherein the hydrochloric acid solution of step (1) is diluted to 3mol/L with 35% analytically pure hydrochloric acid.
3. The rare earth doped bismuth silicate photocatalyst according to claim 1, wherein the tetramethylammonium hydroxide of step (2) is added to deionized water to form a 25% aqueous solution of tetramethylammonium hydroxide.
4. The rare earth element doped bismuth silicate photocatalyst according to claim 1, wherein the rare earth element in the hydrated rare earth nitrate compound of step (2) comprises Ce 3+ 、Pr 3+ 、Er 3+ 、Tm 3+ ，Yb 3+ 、Sm 3+ 、La 3+ 。
5. The rare earth element doped bismuth silicate photocatalyst according to claim 1, wherein the mass ratio of bismuth nitrate to silica in step (2) is 8:1.
6. The rare earth element doped bismuth silicate photocatalyst according to claim 1, wherein: the application method of the catalyst comprises the following steps: weighing the prepared rare earth ion doped bismuth silicate material 0.01 and g, dissolving in 100 and mL deionized water, adding into a photocatalytic reaction device, and adding CO 2 Introducing into a reaction device at a flow rate of 60mL/min, and introducing N 2 50 After the min, a xenon lamp of 300W is used as a simulated light source for irradiation, 1mL samples are collected every 30min, and the concentration of the methanol is analyzed by a gas chromatograph, and the testing method comprises the following steps: the sample injection amount is 1 mu L, the temperature of the vaporization chamber and the detector is 250 ℃, the column temperature is kept at 60 ℃ for 1min, then the sample is kept at 10 ℃/min to 100 ℃ for 1min, and the concentration of methanol in the sample is measured by comparing the peak area with that of a standard sample.
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