CN115745000A - Pt-modified multi-element metal oxide sensitive material and preparation method and application thereof - Google Patents
Pt-modified multi-element metal oxide sensitive material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 80
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 28
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 20
- -1 transition metal salts Chemical class 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 150000002505 iron Chemical class 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 63
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910021381 transition metal chloride Inorganic materials 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 12
- 230000007547 defect Effects 0.000 abstract description 6
- 239000000843 powder Substances 0.000 description 22
- 230000004044 response Effects 0.000 description 20
- 150000002431 hydrogen Chemical class 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011540 sensing material Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 8
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- 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 6
- 239000000725 suspension Substances 0.000 description 6
- 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 5
- 229910017855 NH 4 F Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 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 4
- 102000020897 Formins Human genes 0.000 description 4
- 108091022623 Formins Proteins 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- IIDYTZRUUWUVQF-UHFFFAOYSA-D niobium(5+) pentasulfate Chemical compound [Nb+5].[Nb+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IIDYTZRUUWUVQF-UHFFFAOYSA-D 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses a preparation method of a Pt modified multi-element metal oxide sensitive material, which comprises the following steps: s1: sequentially adding iron salt, a precipitator and one or more other transition metal salts into deionized water, and stirring to obtain a uniformly mixed solution A; s2: putting the mixed solution A into a reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃, and preserving heat for 8-12 h; s3: the material is calcined for 3 hours at 300 ℃ under the air condition after being centrifuged, washed and dried to obtain FeMO x A sensitive material; s4: feMO is mixed x Dispersing the sensitive material in an ethanol solution to obtain a solution B; s5: slowly adding the chloroplatinic acid solution into the solution B drop by drop, stirring, washing and drying; s6: placing the materials in H 2 Heating to 120 deg.C under Ar atmosphere, holding for 2 hr, and cooling to room temperature to obtainPt/FeMO x A sensitive material. The defect types and the number of the prepared gas sensitive materials are increased, and the sensitivity, the stability and the selectivity of the hydrogen sensor prepared by adopting the gas sensitive materials are obviously improved.
Description
Technical Field
The invention belongs to the field of semiconductor metal oxide gas sensors, and particularly relates to a Pt modified multi-element metal oxide sensitive material for improving the performance of a hydrogen sensor, and a preparation method and application thereof.
Background
Hydrogen is a commonly used reducing agent in industrial production and has wide application. It is worth noting that hydrogen is a colorless and odorless gas, and has the characteristics of high diffusivity, high combustion heat and low explosive concentration in air, so that the safety problem of hydrogen in the transportation and use processes is of great concern. The semiconductor metal oxide gas sensor has the advantages of high stability, low cost, simple manufacturing process and the like, so that the semiconductor metal oxide gas sensor is widely applied to detection of toxic gas, flammable and explosive gas and industrial waste gas. However, the sensitive material of the mos gas sensor still faces the problems of low sensitivity, long response/recovery time, and poor selectivity. Therefore, there is a strong interest in developing a gas sensor having high sensitivity, fast response speed, high selectivity and low concentration detection.
In order to develop a semiconductor metal oxide sensitive material with high sensitivity, high response/recovery speed and low concentration detection, chinese patent with application number CN201910260163.6 discloses a Pt modified SnO 2 Method for preparing nano-rod sensitive material and prepared SnO 2 The nano-rods have high length-diameter ratio and Pt nano-particles are uniformly dispersed in SnO by using an ultraviolet light reduction method 2 The nanorod surface enables the sensor to show obvious resistance change under low hydrogen concentration. Chinese patent with application number of CN201110137838.1 discloses Pt and Pd supported TiO 2 The sensitive material is prepared into TiO by twice anodic oxidation of high-purity titanium sheets 2 And then noble metal particles (Pt and Pd) are deposited on the TiO 2 On the nanotubes. Noble metal coating quickens H 2 With TiO 2 The interaction of the nanotube surface improves the sensitivity of hydrogen. The Chinese patent with the application number of CN201510760530.0 discloses a preparation method of Pt/Pd nanoparticle sputtering molybdenum oxide fiber paper, and the sensor prepared by the method can work at normal temperature, and has the advantages of high sensitivity, short response/recovery time and the like. The improvement of the performance of the gas sensor mainly depends on the composition of the noble metal Pt/Pd and the single metal oxide, so that the sensor is improved in the aspects of operation temperature, sensitivity, response/recovery time and the like, but the types and the quantity of defects in the single metal oxide are limited, and the cost of the sensor is increased due to the loading of the noble metal Pt/Pd nanoparticles.
Disclosure of Invention
An object of the present invention is to provide a method for preparing a Pt-modified multi-component metal oxide sensitive material, so as to improve the sensitivity, stability and response/recovery time of a hydrogen sensor.
In order to achieve the above object, the present invention provides a method for preparing a Pt-modified multi-element metal oxide sensitive material, comprising the steps of:
s1: sequentially adding ferric salt, a precipitator and one or more other transition metal salts into deionized water, and stirring to obtain a uniformly mixed solution A;
s2: putting the mixed solution A into a reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃, and preserving heat for 8-12 h;
s3: the material obtained in the step S2 is calcined for 3 hours at 300 ℃ under the air condition after being centrifuged, washed and dried to obtain FeMO x A sensitive material;
s4: feMO obtained in step S3 x Dispersing the sensitive material in an ethanol solution to obtain a uniformly mixed solution B;
s5: slowly and dropwise adding the chloroplatinic acid solution into the solution B, stirring for 3 hours, and then washing and drying;
s6: the material obtained in the step S5 is added into H 2 Heating to 120 ℃ under the Ar atmosphere, preserving heat for 2 hours, and cooling to room temperature to obtain Pt/FeMO x A sensitive material. Wherein,m is other transition metal elements except iron.
Compared with the prior art, the invention selects the Fe with narrow band gap width, high stability, low cost and environmental friendliness 2 O 3 The multi-element metal oxide sensitive material with multiple defects is synthesized in one step by adopting a simple hydrothermal synthesis method, and the noble metal Pt is dispersed on the surface of the metal oxide in an atomic form, so that the gas-sensitive performance of the gas sensor is obviously improved. Compared with the prior sensitive material compounded by Pt/Pd and single metal oxide, the Pt modified multi-element metal oxide sensitive material prepared by the invention has obviously increased defect types and quantity. The preparation method is simple, low in cost, strong in repeatability and free of surfactant.
Preferably, in step S1, the molar ratio of the metal element to the precipitant is 1: (2-5); in the metal elements, the molar ratio of the iron element to other transition metal elements (M) is 1: (1-3).
Preferably, in step S1, the molar ratio of the iron salt, the precipitating agent, the one or more other transition metal salts and the deionized water is 1: (4.36-10): (0 to 3): (2700-4370).
Preferably, in step S5, the concentration of the chloroplatinic acid solution is 50mg mL -1 And the molar ratio of the platinum element in the chloroplatinic acid to the metal element in the solution B is 1: (200-400).
Preferably, in step S1, the iron salt is FeCl 3 、Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 Any one of the above.
Preferably, in step S1, the other transition metal salt is other transition metal chloride or transition metal sulfide except iron salt. Other transition metal salts may be selected such as: transition metal chlorides such as copper chloride, zinc chloride, manganese chloride, chromium chloride, titanium chloride, molybdenum chloride, and tungsten chloride, or transition metal sulfides such as manganese sulfate, zinc sulfate, molybdenum sulfate, niobium sulfate, and copper sulfate.
Preferably, in step S1, the precipitating agent is any one of urea and ammonium fluoride or a mixture of the two.
The invention also provides a Pt modified multi-element metal oxide sensitive material prepared by the preparation method, and compared with the existing Pt/Pd and single metal oxide composite sensitive material, the Pt modified multi-element metal oxide sensitive material has obviously increased defect types and quantity.
The invention also provides application of the Pt modified multi-element metal oxide sensitive material in a hydrogen sensor. The Pt modified multi-element metal oxide sensitive material is used as a gas sensitive material of a hydrogen sensor, so that the sensitivity, response/recovery time, selectivity and stability of the hydrogen sensor can be effectively improved.
The Pt modified multi-element metal oxide sensitive material prepared by the invention has obviously increased defect types and number. The preparation method is simple, low in cost, strong in repeatability and free of surfactant. Experimental test results show that the sensitivity, response/recovery time, selectivity and stability of the Pt modified multi-element metal oxide sensor are remarkably improved compared with those of the existing hydrogen sensor.
Drawings
FIG. 1 shows Fe obtained in comparative example 1 2 O 3 SEM images of sensitive materials;
FIG. 2 shows Pt/Fe obtained in example 1 2 (MoO 4 ) 3 SEM images of sensitive materials;
FIG. 3 shows Pt/ZnFe prepared in example 3 2 O 4 SEM pictures of sensitive materials;
FIG. 4 is a graph showing the sensitivity change of 10ppm hydrogen at different temperatures of hydrogen sensors manufactured using the sensing materials manufactured in example 1, example 2, example 3, comparative example 1 and comparative example 2;
FIG. 5 is a continuous dynamic response curve of a hydrogen sensor made of the sensing material prepared in example 1 at an optimal operating temperature and different hydrogen concentrations;
FIG. 6 is a continuous dynamic response curve of a hydrogen sensor made of the sensing material prepared in example 3 at an optimal operating temperature and different hydrogen concentrations;
FIG. 7 is a continuous dynamic response curve of a hydrogen sensor made with the sensing material made in example 1 at the optimum operating temperature, 10ppm hydrogen concentration;
FIG. 8 is a continuous dynamic response curve of a hydrogen sensor made with the sensing material made in example 3 at an optimum operating temperature and a hydrogen concentration of 10 ppm;
fig. 9 is a graph showing the response value of 10ppm of hydrogen, carbon monoxide and methane at the optimum operating temperature for a hydrogen sensor made using the sensing materials prepared in examples 1 and 3, respectively.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations or modifications made based on the present invention are intended to be within the scope of the present invention. Examples of the present invention are only two Pt modified multi-component metal oxide sensing materials (Pt/Fe) 2 (MoO 4 ) 3 And Pt/ZnFeO 4 ) Without being limited to the two Pt modified multi-element metal oxide sensitive materials, the skilled person can substitute other aliovalent metals doped in alpha-Fe 2 O 3 The amounts of reagents and raw materials used and the experimental conditions in the matrix can also be adjusted within the parameters defined in the claims and should be considered as falling within the scope of the present invention.
In the present invention, the equipment, raw materials and the like used are commercially available or commonly used in the art. The following are the main reagents employed in the examples:
example 1:
Pt/Fe was prepared as follows 2 (MoO 4 ) 3 Sensitive material:
0.41g of Fe (NO) was taken 3 ) 3 ·9H 2 O，3.76g(NH 4 ) 6 Mo 7 O 24 ·4H 2 O，0.116g NH 4 F and 0.308g CN 2 H 4 O (of metal elements with precipitants)The molar ratio is 1:2, the ratio of the iron element to other transition metal elements is 1: 3) And then added to 70mL of deionized water (iron: a precipitant: molybdenum element: the mole ratio of the deionized water is 1:8:3:3851 Stirring for 40min to obtain a uniformly mixed liquid. And putting the uniformly mixed liquid into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃, preserving the heat for 8 hours, naturally cooling to room temperature, washing the obtained suspension with a mixed solution of deionized water and ethanol (3:1) for at least 3 times, and drying at 60 ℃ for 17 hours to obtain a dried powder sample. Finally, calcining the powder sample for 3 hours at 300 ℃ under the air condition, wherein the heating rate is 5 ℃/min, and obtaining Fe 2 (MoO 4 ) 3 A gas sensitive material. Taking 100mgFe 2 (MoO 4 ) 3 Adding the prepared sample into 10mL of ethanol solution, and carrying out ultrasonic and stirring intermittent treatment until Fe 2 (MoO 4 ) 3 The powder was uniformly dispersed in the ethanol solution. 166. Mu.L of 50mg mL of the suspension were taken -1 H of (A) to (B) 2 PtCl 6 A solution (molar ratio of platinum element to transition metal elements (Fe and Mo) of 1 2 (MoO 4 ) 3 The mixture was stirred for 3 hours, washed, and freeze-dried to obtain a powder sample. A sample of the powder obtained above was taken at 10% H 2 Heating to 120 deg.C under Ar atmosphere at a heating rate of 2 deg.C for min -1 Keeping the temperature for 2 hours, and then cooling to room temperature to obtain Pt/Fe 2 (MoO 4 ) 3 A sensitive material.
Example 2:
Pt/Fe was prepared as follows 2 (MoO 4 ) 3 Sensitive material:
0.58g of Fe (NO) was taken 3 ) 3 ·9H 2 O，3.22g(NH 4 ) 6 Mo 7 O 24 ·4H 2 O，0.160g NH 4 F and 0.423g CN 2 H 4 O (molar ratio of metal element to precipitant 1:2.75, molar ratio of iron element to transition metal element 1: 1.8) was sequentially added to 70mL of deionized water (molar ratio of iron element: precipitant: molybdenum element: deionized water 1.7The liquid of (2). And putting the uniformly mixed liquid into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃, preserving the heat for 8 hours, naturally cooling to room temperature, washing the obtained suspension with a mixed solution of deionized water and ethanol (3:1) for at least 3 times, and drying at 60 ℃ for 17 hours to obtain a dried powder sample. Finally, calcining the powder sample for 3 hours at 300 ℃ under the air condition, wherein the heating rate is 5 ℃/min, and obtaining Fe 2 (MoO 4 ) 3 A gas sensitive material. Taking 100mgFe 2 (MoO 4 ) 3 Adding the prepared sample into 10mL of ethanol solution, and carrying out ultrasonic and stirring intermittent treatment until Fe 2 (MoO 4 ) 3 The powder was uniformly dispersed in the ethanol solution. Take 110. Mu.L, 50mg mL -1 H of (A) to (B) 2 PtCl 6 A solution (molar ratio of platinum element to transition metal elements (Fe and Mo) of 1 2 (MoO 4 ) 3 Stirring the mixture for 3 hours, washing, and freeze-drying to obtain a powder sample. A sample of the powder obtained above was taken at 10% H 2 Heating to 120 deg.C under Ar atmosphere at a heating rate of 2 deg.C for min -1 Keeping the temperature for 2 hours, and then cooling to room temperature to obtain Pt/Fe 2 (MoO 4 ) 3 A sensitive material.
Example 3:
Pt/ZnFe is prepared by the following steps 2 O 4 Sensitive material:
0.36g of Fe (NO) was taken 3 ) 3 ·9H 2 O，0.12g ZnCl 2 ，0.116g NH 4 F and 0.364g CN 2 H 4 O (molar ratio of metal element to precipitant is 1:5, and ratio of iron element to transition metal element is 1:1) was sequentially added to 70mL deionized water (molar ratio of iron element: precipitant: molybdenum element: deionized water is 1. And putting the uniformly mixed liquid into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃, preserving the heat for 8 hours, naturally cooling to room temperature, washing the obtained suspension with a mixed solution of deionized water and ethanol (3:1) for at least 3 times, and drying at 60 ℃ for 17 hours to obtain a dried powder sample.Finally, calcining the powder sample for 3 hours at 300 ℃ under the air condition, wherein the heating rate is 5 ℃/min, and obtaining ZnFe 2 O 4 A sensitive material. Taking 100mg of ZnFe 2 O 4 Adding the prepared sample into 10mL of ethanol solution, and carrying out ultrasonic and stirring intermittent treatment until ZnFe is obtained 2 O 4 The powder was uniformly dispersed in the ethanol solution. Take 37.0. Mu.L, 50mg mL -1 H of (A) 2 PtCl 6 (molar ratio of platinum element to transition metal elements (Fe and Zn) is 1: 400) solution was slowly and dropwise added to the above ZnFe 2 O 4 The mixture was stirred for 3 hours, washed, and freeze-dried to obtain a powder sample. A sample of the powder obtained above was taken at 10% H 2 Heating to 120 deg.C under Ar atmosphere at a heating rate of 2 deg.C for min -1 Keeping the temperature for 2 hours, and cooling to room temperature to obtain Pt/ZnFe 2 O 4 A sensitive material.
Comparative example 1:
fe was prepared as follows 2 O 3 Gas sensitive material
Taking 0.41g FeCl 3 ·6H 2 O，0.05g NH 4 F and 0.189g CN 2 H 4 O (molar ratio of metal element to precipitant is 1. And putting the uniformly mixed liquid into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃, preserving the heat for 8 hours, naturally cooling to room temperature, washing the obtained suspension with a mixed solution of deionized water and ethanol (3:1) for at least 3 times, and drying at 60 ℃ for 17 hours to obtain a dried powder sample. Finally, calcining the powder sample for 3 hours at 300 ℃ under the air condition, wherein the heating rate is 5 ℃/min, and obtaining Fe 2 O 3 A sensitive material. Comparative example 2:
Pt/Fe was prepared as follows 2 O 3 Sensitive material:
0.41g of FeCl was taken 3 ·6H 2 O，0.05g NH 4 F and 0.189g CN 2 H 4 O (molar ratio of metal element to precipitant is 1Stirring the mixture in the water (the molar ratio of the iron element to the precipitator to the deionized water is 1. And putting the uniformly mixed liquid into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃, preserving the heat for 8 hours, naturally cooling to room temperature, washing the obtained suspension with a mixed solution of deionized water and ethanol (3:1) for at least 3 times, and drying at 60 ℃ for 17 hours to obtain a dried powder sample. Finally, calcining the powder sample for 3 hours at 300 ℃ under the air condition, wherein the heating rate is 5 ℃/min, and obtaining Fe 2 O 3 A sensitive material. Adding 100mg of the prepared sample into 10mL of ethanol solution, and carrying out ultrasonic and stirring intermittent treatment until Fe is obtained 2 O 3 The powder was uniformly dispersed in the ethanol solution. Collecting 24.0. Mu.L of 50mg mL -1 H of (A) to (B) 2 PtCl 6 (molar ratio of platinum element to Fe element is 1 2 O 3 Stirring the mixture for 3 hours, washing, and freeze-drying to obtain a powder sample. A sample of the powder obtained above was taken at 10% H 2 Heating to 120 deg.C under Ar atmosphere at a heating rate of 2 deg.C for min -1 Keeping the temperature for 2 hours, and then cooling to room temperature to obtain Pt/Fe 2 O 3 A sensitive material.
And (3) analyzing a test result:
from the SEM photograph of FIG. 1, fe obtained in comparative example 1 was observed 2 O 3 The sensitive material mainly exists in the shapes of lines and polyhedrons, and the surface is smooth. As can be seen from the SEM image of FIG. 2, pt/Fe obtained in example 1 2 (MoO 4 ) 3 The sensitive material has a flower-like appearance formed by nano wires and is not in Pt/Fe 2 (MoO 4 ) 3 The presence of Pt nanoparticles was observed on the surface, because Pt was dispersed in Fe in atomic form due to a small amount of Pt supported 2 (MoO 4 ) 3 A surface. As can be seen from the SEM image of FIG. 3, example 3 produced Pt/ZnFe 2 O 4 The sensitive material is formed by stacking nanowires. As can be seen from SEM images of 1-3, fe is successfully prepared by the preparation method provided by the invention 2 O 3 Sensitive material, pt/Fe 2 (MoO 4 ) 3 Sensitive material and Pt/ZnFe 2 O 4 A sensitive material. As can be seen from FIG. 4, fe produced using the sensitive material produced in comparative example 1 2 O 3 Sensor, pt/Fe made of sensitive material prepared in comparative example 2 2 O 3 Sensor, pt/Fe made of sensitive material prepared in example 1 2 (MoO 4 ) 3 Sensor, pt/Fe made of sensitive material prepared in example 2 2 (MoO 4 ) 3 Sensor and Pt/ZnFe made of sensitive material prepared in example 3 2 O 4 The response value of the sensor under the condition of 10ppm hydrogen firstly rises to the maximum value and then falls along with the rise of the temperature. Pt/Fe made of the sensitive Material obtained in example 1 at the same temperature 2 (MoO 4 ) 3 Sensor and Pt/ZnFe made of sensitive material prepared in example 3 2 O 4 Compared with Fe prepared by adopting the sensitive material prepared in the comparative example 1, the sensor has the advantages that 2 O 3 Sensor, pt/Fe made of sensitive material prepared in comparative example 2 2 O 3 Sensor and Pt/Fe made with the sensitive Material obtained in example 2 2 (MoO 4 ) 3 The response value of the sensor is greatly improved. As can be seen from FIG. 5, pt/Fe prepared using the sensing material obtained in example 1 was used at 300 deg.C 2 (MoO 4 ) 3 The response value of the sensor increases as the hydrogen concentration increases. As can be seen from FIG. 6, pt/ZnFe prepared using the sensitive material obtained in example 3 was used at 300 deg.C 2 O 4 The response value of the sensor increases with an increase in the hydrogen concentration. As can be seen from FIG. 7, pt/Fe prepared using the sensing material obtained in example 1 was used under the conditions of 300 ℃ and 10ppm hydrogen gas 2 (MoO 4 ) 3 The hydrogen sensor has high stability and short response/recovery time. As can be seen from FIG. 8, pt/ZnFe produced by using the sensitive material obtained in example 3 was used under the conditions of 300 ℃ and 10ppm hydrogen 2 O 4 The hydrogen sensor has high stability and no baseline shift phenomenon. From the bar chart of FIG. 9, it can be seen that Pt/Fe made with the sensing material obtained in example 1 2 (MoO 4 ) 3 Gas sensorAnd Pt/ZnFe made of the sensitive material obtained in example 3 2 O 4 The selectivity of the gas sensor to hydrogen is high.
The above performance data show that the Pt/Fe prepared in example 2 2 (MoO 4 ) 3 The gas sensor has limited improvement in sensitivity to hydrogen gas, and the Pt-modified multi-component Fe prepared in examples 1 and 3 2 O 3 The base sensitive material is used as the gas sensitive material of the hydrogen sensor, and the prepared hydrogen sensor has obvious advantages in the aspects of response value, stability, response time and selectivity.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
The above description is only a partial example of the present invention, and does not limit the embodiments and the protection scope of the present invention, therefore, it should be recognized that the present invention is covered by the protection scope of the present invention by the equivalent substitution and obvious change made by the description of the present invention for those skilled in the art.
Claims (9)
1. A preparation method of a Pt modified multi-element metal oxide sensitive material is characterized by comprising the following steps: the method comprises the following steps:
s1: sequentially adding ferric salt, a precipitator and one or more other transition metal salts into deionized water, and stirring to obtain a uniformly mixed solution A;
s2: putting the mixed solution A into a reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃, and preserving heat for 8-12 h;
s3: the material obtained in the step S2 is calcined for 3 hours at 300 ℃ under the air condition after being centrifuged, washed and dried to obtain FeMO x A sensitive material;
s4: feMO obtained in step S3 x Dispersing the sensitive material in an ethanol solution to obtain a uniformly mixed solution B;
s5: slowly and dropwise adding the chloroplatinic acid solution into the solution B, stirring for 3 hours, and then washing and drying;
s6: the material obtained in the step S5 is added into H 2 Heating to 120 ℃ under the Ar atmosphere, preserving heat for 2 hours, and cooling to room temperature to obtain Pt/FeMO x A sensitive material.
2. The method of claim 1, wherein: in step S1, the molar ratio of the metal element to the precipitant is 1: (2-5); in the metal elements, the molar ratio of the iron element to other transition metal elements is 1: (1-3).
3. The method of claim 1, wherein: in step S1, the molar ratio of the ferric salt, the precipitating agent, the one or more other transition metal salts, and the deionized water is 1: (4.36-10): (0 to 3): (2700-4370).
4. The method of claim 1, wherein: in step S5, the concentration of the chloroplatinic acid solution is 50mgmL -1 And the molar ratio of the platinum element in the chloroplatinic acid to the metal element in the solution B is 1: (200-400).
5. The method of claim 1, wherein: in step S1, the ferric salt is FeCl 3 、Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 Any one of the above.
6. The method of claim 1, wherein: in step S1, the other transition metal salt is a transition metal chloride or a transition metal sulfide other than the iron salt.
7. The method of claim 1, wherein: in step S1, the precipitating agent is any one of urea and ammonium fluoride or a mixture of both.
8. A Pt modified multi-element metal oxide sensitive material is characterized in that: prepared by the preparation method of any one of claims 1 to 7.
9. Pt modified multi-element Fe 2 O 3 The hydrogen sensor is characterized in that: the gas sensitive material is the Pt modified multi-element metal oxide sensitive material as defined in claim 8.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106198647A (en) * | 2016-07-22 | 2016-12-07 | 武汉工程大学 | A kind of dimethylbenzene gas sensitive, dimethylbenzene gas sensitive device and preparation method thereof |
| CN107459064A (en) * | 2016-06-03 | 2017-12-12 | 中国科学院大连化学物理研究所 | A kind of nanocube accumulates layered mesoporous FeMoO4The preparation method of solid material |
| CN109781800A (en) * | 2019-01-25 | 2019-05-21 | 青岛大学 | A kind of gas sensor and preparation method thereof based on metal molybdate nanocomposite |
| CN110124678A (en) * | 2019-05-29 | 2019-08-16 | 中国矿业大学 | The Fe prepared using waste silicon molybdenum rod2(MoO4)3/MoO3Catalysis material, method and its application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459064A (en) * | 2016-06-03 | 2017-12-12 | 中国科学院大连化学物理研究所 | A kind of nanocube accumulates layered mesoporous FeMoO4The preparation method of solid material |
| CN106198647A (en) * | 2016-07-22 | 2016-12-07 | 武汉工程大学 | A kind of dimethylbenzene gas sensitive, dimethylbenzene gas sensitive device and preparation method thereof |
| CN109781800A (en) * | 2019-01-25 | 2019-05-21 | 青岛大学 | A kind of gas sensor and preparation method thereof based on metal molybdate nanocomposite |
| CN110124678A (en) * | 2019-05-29 | 2019-08-16 | 中国矿业大学 | The Fe prepared using waste silicon molybdenum rod2(MoO4)3/MoO3Catalysis material, method and its application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116514175A (en) * | 2023-05-16 | 2023-08-01 | 中国石油大学(华东) | Preparation method of zinc ferrite/molybdenum oxide nano material, MEMS hydrogen sulfide sensor and application thereof |
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