CN115745000B - Pt-modified multi-metal oxide sensitive material and preparation method and application thereof - Google Patents
Pt-modified multi-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 87
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 22
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 transition metal salts Chemical class 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001354 calcination 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
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 68
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 53
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 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
- 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 1
- 150000002751 molybdenum Chemical class 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 abstract description 15
- 230000035945 sensitivity Effects 0.000 abstract description 13
- 230000007547 defect Effects 0.000 abstract description 7
- 239000000843 powder Substances 0.000 description 22
- 230000004044 response Effects 0.000 description 20
- 150000002431 hydrogen Chemical class 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 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 9
- 238000011084 recovery Methods 0.000 description 8
- 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 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 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
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 102000020897 Formins Human genes 0.000 description 4
- 108091022623 Formins Proteins 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- 239000011540 sensing material Substances 0.000 description 3
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910021381 transition metal chloride Inorganic materials 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
- 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
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application 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
- 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 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
- 239000002440 industrial waste Substances 0.000 description 1
- 230000003993 interaction Effects 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
- 239000011159 matrix material Substances 0.000 description 1
- 239000002923 metal particle Substances 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 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
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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 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: centrifuging, washing and drying the material, and calcining at 300 ℃ under air condition for 3 hours to obtain FeMO x A sensitive material; s4: feMO is added to 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 dropwise, stirring, washing and drying; s6: putting the materials in H 2 Heating to 120 ℃ in Ar atmosphere, preserving heat for 2 hours, and cooling to room temperature to obtain Pt/FeMO x Sensitive material. The defect types and the defect number of the prepared gas-sensitive material are increased, and the sensitivity, the stability and the selectivity of the hydrogen sensor prepared from the sensitive material 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 reducing agent commonly used in industrial production and has wide application. It is notable that hydrogen is a colorless and odorless gas, and has the characteristics of high diffusivity, high combustion heat and low explosion concentration in air, so that the safety problem of hydrogen in the transportation and use processes is greatly concerned. The semiconductor metal oxide gas sensor is widely applied to detection of toxic gas, inflammable and explosive gas and industrial waste gas due to the advantages of high stability, low cost, simple manufacturing process and the like. However, the sensitive materials of the semiconductor metal oxide gas sensor still face the problems of low sensitivity, long response/recovery time, poor selectivity and the like, and need to be solved. Therefore, there has been a great deal of attention in developing a gas sensor having high sensitivity, high 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 application No. CN201910260163.6 discloses a Pt modified SnO 2 Preparation method of nanorod sensitive material and prepared SnO 2 The length-diameter ratio of the nano rod is high, and Pt nano particles are uniformly dispersed in SnO by using an ultraviolet light reduction method 2 The surface of the nano rod enables the sensor to show obvious resistance change under the condition of lower hydrogen concentration. Chinese patent application No. CN201110137838.1 discloses a Pt and Pd supported TiO 2 The composite sensitive material of the (2) is prepared into TiO by anodic oxidation of high-purity titanium sheets twice 2 Then noble metal particles (Pt and Pd) are deposited on the TiO 2 On the nanotubes. Noble metal coating accelerates H 2 With TiO 2 The interaction of the surfaces of the nanotubes improves the sensitivity of hydrogen. The Chinese patent with the application number of CN201510760530.0 discloses a preparation method of Pt/Pd nanoparticle sputtered molybdenum oxide fiber paper, and the sensor prepared by the method can work at normal temperature, 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 combination of the noble metal Pt/Pd and the single metal oxide, so that the sensor is improved in the aspects of operating temperature, sensitivity, response/recovery time and the like, but the single metal element oxide has limited types and quantity of defects, and the loading of the noble metal Pt/Pd nano particles can increase the cost of the sensor.
Disclosure of Invention
The invention aims at solving the technical problems, and provides a preparation method of a Pt modified multi-element 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: centrifuging, washing and drying the material obtained in the step S2, and calcining for 3 hours at 300 ℃ under the air condition to obtain FeMO x A sensitive material;
s4: the FeMO obtained in the step S3 is added 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, washing and drying;
s6: the material obtained in the step S5 is treated in H 2 Heating to 120 ℃ in Ar atmosphere, preserving heat for 2 hours, and cooling to room temperature to obtain Pt/FeMO x Sensitive material. Wherein M refers to other transition metal elements except iron.
Compared with the prior art, the invention selects Fe with narrow band gap width, high stability, low cost and environmental friendliness 2 O 3 The method is characterized in that the method is used for preparing a substrate, doping with other aliovalent metals, a simple hydrothermal synthesis method is adopted, a multi-element metal oxide sensitive material with multiple defects is synthesized in one step, noble metal Pt is dispersed on the surface of the metal oxide in an atomic form, and the gas sensitivity of the gas sensor is remarkably improved. Compared with the existing Pt/Pd and single metal oxide composite sensitive material, the Pt modified multi-metal oxide sensitive material prepared by the invention has obviously increased defect types and quantity. The preparation method is simple, low in cost, high in repeatability and free of surfactant.
Preferably, in step S1, the molar ratio of the metal element to the precipitant is 1: (2-5); the molar ratio of the iron element to the other transition metal element (M) among the metal elements is 1: (1-3).
Preferably, in step S1, the molar ratio of the iron salt, the precipitant, the one or more other transition metal salts and deionized water is 1: (4.36-10): (0-3): (2700 to 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 them.
Preferably, in step S1, the other transition metal salt is other transition metal chloride or transition metal sulfide than iron salt. Other transition metal salts may be selected from the group consisting of: 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 ammonia fluoride or a mixture of both.
The invention also provides the Pt modified multi-element metal oxide sensitive material prepared by the preparation method, which has obviously increased defect types and quantity compared with the existing Pt/Pd and single metal oxide composite sensitive material.
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 obvious increase in defect types and quantity. The preparation method is simple, low in cost, high in repeatability and free of surfactant. Experimental test results show that compared with the existing hydrogen sensor, the Pt modified multi-element metal oxide sensor has the advantages of obviously improving sensitivity, response/recovery time, selectivity and stability.
Drawings
FIG. 1 shows Fe obtained in comparative example 1 2 O 3 SEM images of sensitive materials;
FIG. 2 shows Pt/Fe as prepared in example 1 2 (MoO 4 ) 3 SEM images of sensitive materials;
FIG. 3 is a Pt/ZnFe alloy prepared in example 3 2 O 4 SEM images of sensitive materials;
FIG. 4 is a graph showing the sensitivity change of a hydrogen sensor prepared using the sensitive materials prepared in example 1, example 2, example 3, comparative example 1 and comparative example 2 to 10ppm hydrogen at different temperatures;
FIG. 5 is a graph showing the continuous dynamic response of a hydrogen sensor made of the sensitive material prepared in example 1 at different hydrogen concentrations at optimum operating temperatures;
FIG. 6 is a graph showing the continuous dynamic response of a hydrogen sensor made of the sensing material prepared in example 3 at different hydrogen concentrations at optimum operating temperatures;
FIG. 7 is a graph showing the continuous dynamic response of a hydrogen sensor made of the sensing material prepared in example 1 at an optimum operating temperature and a hydrogen concentration of 10 ppm;
FIG. 8 is a graph showing the continuous dynamic response of a hydrogen sensor made of the sensing material prepared in example 3 at an optimum operating temperature and a hydrogen concentration of 10 ppm;
FIG. 9 is a graph showing the response values of hydrogen sensors made of the sensitive materials prepared in example 1 and example 3, respectively, to 10ppm hydrogen, carbon monoxide and methane at the optimal operating temperature.
Detailed Description
The invention will be further illustrated with reference to specific examples. It should be understood that the practice of the invention is not limited to the following examples, but is intended to be within the scope of the invention in any form or modification thereof. As examples of the present invention, only two Pt-modified multi-metal oxide sensitive materials (Pt/Fe 2 (MoO 4 ) 3 And Pt/ZnFeO 4 )，Not limited to the two Pt-modified multi-metal oxide sensitive materials, those skilled in the art may substitute other heterovalent metals doped in α -Fe 2 O 3 The amounts of reagents and materials used in the matrix, as well as the experimental conditions, may be adjusted within the parameters defined in the claims and should be considered as falling within the scope of the invention.
In the present invention, the equipment, raw materials, etc. used are commercially available or commonly used in the art. The following are the main reagents used in the examples:
example 1:
the Pt/Fe is prepared according to the following steps 2 (MoO 4 ) 3 Sensitive material:
0.41g of Fe (NO) 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 (the molar ratio of the metal element to the precipitant is 1:2, the molar ratio of the iron element to other transition metal elements is 1:3) is sequentially added into 70mL of deionized water (the molar ratio of the iron element to the precipitant to the molybdenum element to the deionized water is 1:8:3:3851), and the mixture is stirred for 40min to obtain uniformly mixed liquid. And (3) placing the uniformly mixed liquid into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃, preserving 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 at 300 ℃ for 3 hours under the air condition, wherein the heating rate is 5 ℃/min, and obtaining Fe 2 (MoO 4 ) 3 A gas sensitive material. Taking 100mg Fe 2 (MoO 4 ) 3 Adding the prepared sample into 10mL of ethanol solution, and intermittently treating with ultrasound and stirring to obtain Fe 2 (MoO 4 ) 3 The powder was uniformly dispersed in the ethanol solution. Taking 166 mu L and 50mg mL -1 H of (2) 2 PtCl 6 The solution (molar ratio of platinum element to transition metal element (Fe and Mo) is 1:200) was slowly and dropwise added to the above Fe 2 (MoO 4 ) 3 Is stirred for 3 hours, and then washed and freeze-dried to obtain a powder sample. The powder sample obtained above was subjected to a reaction at 10% H 2 Heating to 120deg.C under Ar atmosphere at a heating rate of 2deg.C for min -1 After 2 hours of heat preservation, cooling to room temperature to obtain Pt/Fe 2 (MoO 4 ) 3 Sensitive material.
Example 2:
the Pt/Fe is prepared according to the following steps 2 (MoO 4 ) 3 Sensitive material:
0.58g of Fe (NO) 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 (the molar ratio of the metal element to the precipitant is 1:2.75, the molar ratio of the iron element to the transition metal element is 1:1.8) is sequentially added into 70mL of deionized water (the molar ratio of the iron element to the precipitant to the molybdenum element to the deionized water is 1:7.7:1.8:2700), and the mixture is stirred for 40min to obtain uniformly mixed liquid. And (3) placing the uniformly mixed liquid into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃, preserving 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 at 300 ℃ for 3 hours under the air condition, wherein the heating rate is 5 ℃/min, and obtaining Fe 2 (MoO 4 ) 3 A gas sensitive material. Taking 100mg Fe 2 (MoO 4 ) 3 Adding the prepared sample into 10mL of ethanol solution, and intermittently treating with ultrasound and stirring to obtain Fe 2 (MoO 4 ) 3 The powder was uniformly dispersed in the ethanol solution. Taking 110 mu L and 50mg mL -1 H of (2) 2 PtCl 6 The solution (molar ratio of platinum element to transition metal element (Fe and Mo) was 1:300) was slowly and dropwise added to the above Fe 2 (MoO 4 ) 3 Is stirred for 3 hours and then washedAnd freeze-drying to obtain a powder sample. The powder sample obtained above was subjected to a reaction at 10% H 2 Heating to 120deg.C under Ar atmosphere at a heating rate of 2deg.C for min -1 After 2 hours of heat preservation, cooling to room temperature to obtain Pt/Fe 2 (MoO 4 ) 3 Sensitive material.
Example 3:
the Pt/ZnFe is prepared according to the following steps 2 O 4 Sensitive material:
0.36g of Fe (NO) 3 ) 3 ·9H 2 O，0.12g ZnCl 2 ，0.116g NH 4 F and 0.364g CN 2 H 4 O (the molar ratio of the metal element to the precipitator is 1:5, the molar ratio of the iron element to the transition metal element is 1:1) is sequentially added into 70mL of deionized water (the molar ratio of the iron element to the precipitator to the molybdenum element to the deionized water is 1:10:1:4370), and the mixture is stirred for 40min to obtain uniformly mixed liquid. And (3) placing the uniformly mixed liquid into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃, preserving 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 at 300 ℃ for 3 hours under the air condition, wherein the heating rate is 5 ℃/min, and obtaining ZnFe 2 O 4 Sensitive material. 100mg ZnFe is taken 2 O 4 Adding the prepared sample into 10mL of ethanol solution, and intermittently treating with ultrasound and stirring to ZnFe 2 O 4 The powder was uniformly dispersed in the ethanol solution. Taking 37.0 mu L and 50mg mL -1 H of (2) 2 PtCl 6 The (platinum element to transition metal element (Fe and Zn) molar ratio of 1:400) solution was slowly and dropwise added to the above ZnFe 2 O 4 Is stirred for 3 hours, and then washed and freeze-dried to obtain a powder sample. The powder sample obtained above was subjected to a reaction at 10% H 2 Heating to 120deg.C under Ar atmosphere at a heating rate of 2deg.C for min -1 After 2 hours of heat preservation, cooling to room temperature to obtain Pt/ZnFe 2 O 4 Sensitive material.
Comparative example 1:
the method comprises the following steps ofPreparation of Fe 2 O 3 Gas-sensitive material
0.41g 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 1:4.36) is added into 70mL deionized water in turn (molar ratio of iron element to precipitant to deionized water is 1:4.36:3851), and stirred for 40min to obtain uniformly mixed liquid. And (3) placing the uniformly mixed liquid into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃, preserving 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 at 300 ℃ for 3 hours under the air condition, wherein the heating rate is 5 ℃/min, and obtaining Fe 2 O 3 Sensitive material. Comparative example 2:
the Pt/Fe is prepared according to the following steps 2 O 3 Sensitive material:
0.41g 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 1:4.36) is added into 70mL deionized water in turn (molar ratio of iron element to precipitant to deionized water is 1:4.36:3851), and stirred for 40min to obtain uniformly mixed liquid. And (3) placing the uniformly mixed liquid into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃, preserving 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 at 300 ℃ for 3 hours under the air condition, wherein the heating rate is 5 ℃/min, and obtaining Fe 2 O 3 Sensitive material. Adding 100mg of the prepared sample into 10mL of ethanol solution, and intermittently treating with ultrasound and stirring until Fe is obtained 2 O 3 The powder was uniformly dispersed in the ethanol solution. Taking 24.0 mu L and 50mg mL -1 H of (2) 2 PtCl 6 The (molar ratio of platinum element to Fe element is 1:350) solution is slowly and dropwise added to the above Fe 2 O 3 Is stirred for 3 hours and then washedAnd freeze-drying to obtain a powder sample. The powder sample obtained above was subjected to a reaction at 10% H 2 Heating to 120deg.C under Ar atmosphere at a heating rate of 2deg.C for min -1 After 2 hours of heat preservation, cooling to room temperature to obtain Pt/Fe 2 O 3 Sensitive material.
Analysis of test results:
from the SEM image of FIG. 1, it can be observed that Fe was prepared in comparative example 1 2 O 3 The sensitive material mainly exists in the shape of a linear shape and a polyhedral shape, and the surface is smooth. As can be seen from the SEM image of FIG. 2, pt/Fe prepared in example 1 2 (MoO 4 ) 3 The sensitive material has a flower-like morphology formed by nano wires and is not in Pt/Fe 2 (MoO 4 ) 3 The presence of Pt nanoparticles was observed on the surface due to the small Pt loading, pt being dispersed in the form of atoms in Fe 2 (MoO 4 ) 3 A surface. As can be seen from the SEM image of FIG. 3, pt/ZnFe prepared in example 3 2 O 4 The sensitive material is formed by stacking nanowires. As can be seen from SEM images of 1-3, the preparation method provided by the invention successfully prepares Fe 2 O 3 Sensitive material, pt/Fe 2 (MoO 4 ) 3 Sensitive material and Pt/ZnFe 2 O 4 Sensitive material. As can be seen from FIG. 4, fe made of the sensitive material obtained 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 is increased to the maximum value and then decreased with the increase of the temperature under the condition of 10ppm hydrogen. Pt/Fe made of the sensitive material prepared 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 made of the sensitive material prepared in comparative example 1 2 O 3 Sensor, pt/Fe made of sensitive material prepared in comparative example 2 2 O 3 Sensor and Pt/Fe made of sensitive material prepared in example 2 2 (MoO 4 ) 3 The response value of the sensor is greatly improved. As can be seen from FIG. 5, at 300℃Pt/Fe is produced using the sensitive material produced in example 1 2 (MoO 4 ) 3 The response value of the sensor increases with an increase in the hydrogen concentration. As can be seen from FIG. 6, at 300℃Pt/ZnFe prepared from the sensitive material prepared in example 3 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 was prepared using the sensitive material prepared in example 1 at 300℃and 10ppm hydrogen 2 (MoO 4 ) 3 The hydrogen sensor has high stability and short response/recovery time. As can be seen from FIG. 8, pt/ZnFe prepared from the sensitive material prepared in example 3 at 300℃and 10ppm hydrogen 2 O 4 The hydrogen sensor has high stability and no baseline shift phenomenon. As can be seen from the bar chart of FIG. 9, pt/Fe made of the sensitive material prepared in example 1 2 (MoO 4 ) 3 Gas sensor and Pt/ZnFe made of sensitive material prepared in example 3 2 O 4 The gas sensor has high selectivity to hydrogen.
The above performance data indicate that Pt/Fe prepared in example 2 2 (MoO 4 ) 3 The gas sensor had limited improvement in hydrogen sensitivity, and Pt-modified multi-element Fe prepared in example 1 and example 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.
The invention is not limited to the use of the description and embodiments listed, which can be applied to various fields suitable for the invention, and further modifications and variations can be easily realized by those skilled in the art without departing from the spirit and the essence of the invention, but these corresponding modifications and variations shall fall within the scope of protection claimed by the invention.
The above description is only a few examples of the present invention and is not intended to limit the embodiments and the protection scope of the present invention, and it should be appreciated by those skilled in the art that equivalent substitutions and obvious changes made by the content of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A preparation method of a Pt modified multi-element metal oxide sensitive material is characterized by comprising the following steps of: the method comprises the following steps:
s1: sequentially adding ferric salt, a precipitator and molybdenum salt into deionized water, and stirring to obtain a uniformly mixed solution A; the molar ratio of the metal element to the precipitant is 1: (2-5); the molar ratio of the iron element to the molybdenum element is 1: (1-3);
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: centrifuging, washing and drying the material obtained in the step S2, and calcining 3h at 300 ℃ under the air condition to obtain Fe 2 (MoO 4 ) 3 A gas sensitive material;
s4: fe obtained in step S3 2 (MoO 4 ) 3 Dispersing the gas-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, washing and drying; the concentration of the chloroplatinic acid solution was 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);
s6: the material obtained in the step S5 is treated in H 2 Heating to 120 ℃ in Ar atmosphere, preserving heat for 2 hours, and cooling to room temperature to obtain Pt/Fe 2 (MoO 4 ) 3 Sensitive material.
2. The method of manufacturing according to claim 1, characterized in that: in step S1, the ferric salt is FeCl 3 、Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 Any one of them.
3. The method of manufacturing according to claim 1, characterized in that: in step S1, the precipitant is any one of urea and ammonium fluoride or a mixture of both.
4. A Pt-modified multi-metal oxide sensitive material, characterized in that: the method for preparing the composite material according to any one of claims 1 to 3.
5. Pt modified multielement Fe 2 O 3 The base hydrogen sensor is characterized in that: the gas-sensitive material is the Pt-modified multi-element metal oxide sensitive material as claimed in claim 4.
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| 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 |
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| 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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| 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 |
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