CN114577860B - Metal oxide low-temperature hydrogen sensitive material and preparation method thereof - Google Patents
Metal oxide low-temperature hydrogen sensitive material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000001257 hydrogen Substances 0.000 title claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 45
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 22
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title claims 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims abstract description 8
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 7
- 239000008103 glucose Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 5
- 238000001953 recrystallisation Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 5
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 24
- 230000004044 response Effects 0.000 abstract description 19
- 150000002431 hydrogen Chemical class 0.000 abstract description 12
- 238000001514 detection method Methods 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000003795 desorption Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 description 22
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000009610 hypersensitivity Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a metal oxide low-temperature hydrogen sensitive material and a preparation method thereof. The material is made of SnO doped with Mo element 2 Is compounded with the reduced graphene oxide. The preparation method comprises the following steps: carrying out hydrothermal reaction on glucose solution, and carrying out hydrothermal product and SnCl 2 Dissolving urea and ammonium molybdate tetrahydrate in deionized water, stirring, separating, washing and drying; and (3) carrying out heat treatment and recrystallization on the obtained product, adding a mixed aqueous solution of the crystallized product and GO into a container, stirring, separating, washing and drying the product, and placing the dried product into a tubular furnace, and carrying out high-temperature heat treatment under the hydrogen argon atmosphere for reduction to obtain the hydrogen sensitive material. The hydrogen sensitive material is porous and spherical, has high porosity and specific surface area, is favorable for surface gas adsorption and desorption, can realize the detection of hydrogen at low temperature, has good selective detectability for hydrogen, and has ultra-fast response and recovery detection characteristics.
Description
Technical Field
The invention belongs to the field of semiconductor gas sensitive materials, and particularly relates to a method for detecting low-temperature hydrogen gasUltrasensitive metal oxide Mo-SnO 2 @rgo nanocomposite.
Background
The semiconductor gas sensor is a gas sensor using a semiconductor gas-sensitive material as a sensitive material, is the most common gas sensor, and is widely applied to small molecule gas detection in families, factories and the like, wherein metal oxide is the semiconductor gas-sensitive material with the most wide application due to good stability and high sensitivity. The high-performance metal oxide gas sensitive material is prepared to design a small, cheap and rapid gas sensor, and has important significance for realizing low-temperature and real-time detection of small molecular gases such as hydrogen and the like.
SnO 2 Is often used for gas sensitive materials due to low cost, simple preparation method, high sensitivity for detecting gas, but is usually SnO 2 The working temperature of the gas sensor is higher (200-500 ℃), so that the gas sensor has high energy consumption and is unfavorable for detecting flammable gases such as hydrogen and the like. The optimal working temperature of the single metal oxide can be reduced by element doping, and the doped element has chemical sensitization and electronic sensitization, thereby being beneficial to the adsorption, activation and reaction of gas molecules on the surface of the sensitive material. Meanwhile, the reduced graphene oxide can provide larger specific surface area and better conductivity so as to improve the gas-sensitive performance of the small molecule gas. In contrast, the invention adopts the impregnation calcination method to prepare Mo-SnO with low-temperature sensitive hydrogen gas detection characteristic for the first time 2 @ rGO composite.
Disclosure of Invention
Aiming at the defects of the prior art, the invention prepares the Mo-SnO 2 The @ rGO metal oxide nanocomposite material achieves a fast response and good selective detection of hypersensitivity to hydrogen gas at low temperatures.
The invention provides a metal oxide low-temperature hydrogen sensitive material, which comprises reduced graphene oxide and SnO doped with Mo element 2 The reduced graphene oxide uniformly coats the Mo element doped SnO 2 。
Preferably, the material has a porous spherical structure.
The invention also provides a preparation method of the metal oxide low-temperature hydrogen sensitive material, which comprises the following specific steps:
1) Glucose is dissolved in deionized water, the obtained solution is subjected to hydrothermal reaction, and after the reaction is finished, products are separated and washed;
2) Washing the washed hydrothermal product and SnCl 2 Dissolving urea in deionized water, adding ammonium molybdate tetrahydrate, stirring for 6-8h, separating, washing and drying;
3) Placing the dried product in the step 2) into heating equipment for heat treatment and recrystallization to obtain Mo-hollow SnO 2 A porous sphere material;
4) Mo-hollow SnO 2 Dissolving the porous ball material in deionized water, mixing with GO aqueous solution, adding into a container, stirring, separating the product, washing, and oven drying;
5) And (3) placing the dried product in the step (4) in a tube furnace, and carrying out high-temperature heat treatment under hydrogen-argon atmosphere for reduction to finally obtain the metal oxide low-temperature hydrogen sensitive material.
Preferably, in step 1), the mass ratio of the glucose to the deionized water is 1:12.
Preferably, in step 1), the temperature of the hydrothermal reaction is 170-190 ℃ and the reaction time is 5-7h.
Preferably, in step 2), snCl 2 And urea in a molar ratio of 1:2-1:1, hydrothermal product and SnCl 2 The molar ratio of (2) to (1:1) to (2:1), ammonium molybdate tetrahydrate and SnCl 2 The molar ratio of (2) is 1:100-3:100.
Preferably, in step 3), the temperature of the heat treatment is 500-600 ℃, and the heat treatment time is 2-4h.
Preferably, in the mixed solution of step 4), mo-hollow SnO 2 The mass ratio of porous sphere material to GO was 100:1.5.
Preferably, in step 5), the temperature of the high-temperature heat treatment is 200-300 ℃, and the heat treatment time is 1-3h.
Compared with the prior art, the invention has the beneficial effects that:
1) Mo-SnO prepared by the invention 2 The @ rGO nano composite material is porous spherical,the porous structure can increase the porosity, has high specific surface area, is favorable for surface gas adsorption and desorption, and obtains good gas sensitivity.
2) Mo-SnO prepared in the present invention 2 The @ rGO nanocomposite realizes the detection of hydrogen at low temperature;
3) Mo-SnO prepared in the present invention 2 The @ rGO nanocomposite has good selective detectability for hydrogen;
4) Mo-SnO prepared in the present invention 2 The @ rGO nanocomposite has ultra-fast response to hydrogen and recovery detection characteristics.
Drawings
FIG. 1 Mo-SnO prepared in example 1 2 A @ rGO nanocomposite surface topography map;
FIG. 2 Mo-SnO prepared in example 1 2 Comparison of responses to 200ppm different gases at room temperature for @ rGO nanocomposite;
FIG. 3 Mo-SnO prepared in example 1 2 Response of @ rGO nanocomposite to 200ppm hydrogen at different voltages;
FIG. 4 Mo-SnO prepared in example 1 2 Response of @ rGO nanocomposite to 200ppm hydrogen at room temperature.
FIG. 5 Mo-SnO prepared in example 2 2 Response of @ rGO nanocomposite to hydrogen at different concentrations at 150 ℃;
FIG. 6 Mo-SnO prepared in example 3 2 Response of @ rGO nanocomposite to 200ppm hydrogen at 150 ℃.
Detailed Description
Example 1
1) Dissolving 5.40g of glucose in 60mL of deionized water, stirring at room temperature to form a transparent solution, loading into a reaction kettle, carrying out hydrothermal reaction in a reaction kettle oven at 180 ℃ for 6 hours, centrifuging the product after the hydrothermal reaction, and washing with ethanol for 3 times;
2) Washing the hot water product, 3.38g SnCl 2 ·2H 2 Dissolving O and 0.90g of urea in 60mL of deionized water, adding 0.0795g of ammonium molybdate tetrahydrate, stirring for 8 hours, separating, washing and drying;
3) Placing the dried product in a muffle furnace for heat treatment and recrystallization, wherein the temperature of the high-temperature heat treatment is 500 ℃, and the heat treatment time is 2 hours;
4) Dissolving the heat-treated product in deionized water, adding 5mL of GO aqueous solution (1 mol/L) into a beaker, stirring, and separating, washing and drying the product;
5) Placing the dried product into a tubular furnace, and reducing for 2 hours at 300 ℃ in hydrogen argon atmosphere to finally obtain the required Mo-SnO 2 @rgo nanocomposite.
Mo-SnO prepared in example 1 2 The surface morphology of the@rGO nanocomposite is shown in figure 1, and the microstructure can show that the nanocomposite is porous and spherical, the porous structure can increase the porosity, and the nanocomposite has a high specific surface area, is favorable for surface gas adsorption and desorption, and obtains good gas sensitivity.
Mo-SnO prepared in example 1 2 Comparison of response values for 200ppm of different gases at room temperature for the rGO nanocomposite as shown in figure 2, the composite had good selectivity for hydrogen at room temperature.
Mo-SnO prepared in example 1 2 The response of the @ rGO nanocomposite to 200ppm hydrogen at different voltages is shown in figure 3. The operating temperature is determined by the applied voltage, the higher the operating temperature. The response value of the material was 40 when it was operated at 0V heating, i.e. room temperature. The optimum operating temperature is 150 ℃, i.e. 1V heating.
Mo-SnO prepared in example 1 2 The repeatability curve of the @ rGO nanocomposite material at room temperature for 200ppm hydrogen is shown in FIG. 4, and when the material encounters hydrogen, the current value rises rapidly (the resistance decreases), and the response is very rapid; after hydrogen is removed, the current value is quickly restored to the initial value. In 10 times of repeated tests, the response value of the material to 200ppm of hydrogen is not obviously attenuated, which indicates that the material has good repeatability.
Example 2
This example is similar to example 1, except that the washed hydrothermal product, 3.38g SnCl, is taken in step 2) 2 ·2H 2 O and 1.80g of urea were dissolved in 60mL of deionized water and added0.0795g of ammonium molybdate tetrahydrate, stirring for 8 hours, separating, washing and drying; and 5) placing the dried product in a tube furnace, and reducing for 2 hours at 350 ℃ in an argon hydrogen atmosphere.
Mo-SnO prepared in example 2 2 The response of the @ rGO nanocomposite to different concentrations of hydrogen at 150 ℃ is shown in figure 5. The response of the material to hydrogen gas at gas concentrations of 50, 100, 200, 500, 1000ppm increases with increasing gas concentration, and the current value can be quickly restored to the initial value after hydrogen gas removal (the subgraph in fig. 5 is an enlargement of the dashed box portion).
Example 3
This example is similar to example 1, except that in step 3) the dried product is recrystallized by heat treatment in a muffle furnace, wherein the temperature of the high temperature heat treatment is 600 ℃ and the heat treatment time is 2h; and 5) placing the dried product in a tube furnace, and reducing for 1h at 200 ℃ in an argon hydrogen atmosphere.
FIG. 6 shows Mo-SnO in example 3 2 Response of @ rGO nanocomposite to 200ppm hydrogen at 150 ℃. During 13 cycles, when the material encounters hydrogen, the current value rises rapidly (the resistance decreases), and the response is very rapid; after hydrogen is removed, the current value is quickly restored to the initial value. The response was somewhat attenuated, about 20%.
The invention adopts dynamic gas distribution method to measure Mo-SnO 2 The gas sensitive properties of the @ rGO nanocomposite, the response values were defined as:
wherein I is s Indicating the current value of the gas sensor in the gas to be detected with a certain concentration, I 0 The current value of the gas sensor in the air is indicated.
The foregoing detailed description is provided to illustrate the present invention and not to limit the invention, and any modifications and changes made to the present invention within the spirit of the present invention and the scope of the appended claims fall within the scope of the present invention.
Claims (9)
1. A metal oxide low-temperature hydrogen sensitive material is characterized by comprising reduced graphene oxide and SnO doped with Mo element 2 The reduced graphene oxide coats the SnO doped with the Mo element 2 The preparation method of the material comprises the following steps:
1) Glucose is dissolved in deionized water, the obtained solution is subjected to hydrothermal reaction, and after the reaction is finished, products are separated and washed;
2) Washing the washed hydrothermal product and SnCl 2 Dissolving urea in deionized water, adding ammonium molybdate tetrahydrate, stirring for 6-8h, separating, washing and drying;
3) Placing the dried product in the step 2) into heating equipment for heat treatment and recrystallization to obtain Mo-hollow SnO 2 A porous sphere material;
4) Mo-hollow SnO 2 Dissolving the porous ball material in deionized water, mixing with GO aqueous solution, adding into a container, stirring, separating the product, washing, and oven drying;
5) And (3) placing the dried product in the step (4) in a tube furnace, and carrying out high-temperature heat treatment under hydrogen-argon atmosphere for reduction to finally obtain the metal oxide low-temperature hydrogen sensitive material.
2. The metal oxide low temperature hydrogen sensitive material of claim 1, wherein the material has a porous spherical structure.
3. The method for preparing a metal oxide low-temperature hydrogen sensitive material according to claim 1, comprising the following specific steps:
1) Glucose is dissolved in deionized water, the obtained solution is subjected to hydrothermal reaction, and after the reaction is finished, products are separated and washed;
2) Washing the washed hydrothermal product and SnCl 2 Dissolving urea in deionized water, adding ammonium molybdate tetrahydrate, stirring for 6-8h, separating, washing and drying;
3) Baking in the step 2)The dried product is placed into heating equipment for heat treatment and recrystallization to obtain Mo-hollow SnO 2 A porous sphere material;
4) Mo-hollow SnO 2 Dissolving the porous ball material in deionized water, mixing with GO aqueous solution, adding into a container, stirring, separating the product, washing, and oven drying;
5) And (3) placing the dried product in the step (4) in a tube furnace, and carrying out high-temperature heat treatment under hydrogen-argon atmosphere for reduction to finally obtain the metal oxide low-temperature hydrogen sensitive material.
4. The method for preparing a metal oxide low temperature hydrogen sensitive material according to claim 3, wherein in the step 1), the mass ratio of glucose to deionized water is 1:12.
5. The method for preparing a metal oxide low temperature hydrogen sensitive material according to claim 3, wherein in the step 1), the hydrothermal reaction temperature is 170-190 ℃ and the reaction time is 5-7h.
6. The method for preparing a metal oxide low-temperature hydrogen-sensitive material according to claim 3, wherein in step 2), snCl 2 And urea in a molar ratio of 1:2-1:1, hydrothermal product and SnCl 2 The molar ratio of (2) to (1:1) to (2:1), ammonium molybdate tetrahydrate and SnCl 2 The molar ratio of (2) is 1:100-3:100.
7. The method for preparing a metal oxide low temperature hydrogen sensitive material according to claim 3, wherein in the step 3), the temperature of the heat treatment is 500-600 ℃, and the heat treatment time is 2-4h.
8. The method for preparing a metal oxide low-temperature hydrogen-sensitive material according to claim 3, wherein Mo-hollow SnO is contained in the mixed solution of step 4) 2 The mass ratio of porous sphere material to GO was 100:1.5.
9. The method for preparing a metal oxide low temperature hydrogen sensitive material according to claim 3, wherein in the step 5), the high temperature heat treatment is performed at 200-300 ℃ for 1-3h.
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