WO2022142170A1 - Preparation of manganese(iii) oxide atom cluster modified cobaltosic oxide nano-material for detection, and product and application thereof - Google Patents
Preparation of manganese(iii) oxide atom cluster modified cobaltosic oxide nano-material for detection, and product and application thereof Download PDFInfo
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- WO2022142170A1 WO2022142170A1 PCT/CN2021/100421 CN2021100421W WO2022142170A1 WO 2022142170 A1 WO2022142170 A1 WO 2022142170A1 CN 2021100421 W CN2021100421 W CN 2021100421W WO 2022142170 A1 WO2022142170 A1 WO 2022142170A1
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 28
- 238000001514 detection method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title abstract description 4
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 title abstract 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 84
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 53
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000001868 cobalt Chemical class 0.000 claims abstract description 27
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910020632 Co Mn Inorganic materials 0.000 claims abstract description 18
- 229910020678 Co—Mn Inorganic materials 0.000 claims abstract description 18
- 239000012697 Mn precursor Substances 0.000 claims abstract description 18
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 150000002696 manganese Chemical class 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000011572 manganese Substances 0.000 claims description 14
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 2
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 32
- 230000035945 sensitivity Effects 0.000 description 16
- 230000004044 response Effects 0.000 description 13
- 241000238631 Hexapoda Species 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011896 sensitive detection Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 206010019233 Headaches Diseases 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
Definitions
- the invention relates to a preparation method of a gas-sensing material, in particular to a preparation method of a dimanganese trioxide atomic cluster modified cobalt tetroxide nanometer material for detection, its product and its application. Especially for highly sensitive detection of acetone and formaldehyde gas.
- Volatile organic compounds commonly used in chemical materials have caused serious pollution to the human living environment. Long-term exposure to toxic gases can cause headaches, nausea and other symptoms, and even cause cancer in severe cases. Therefore, it is imperative to strengthen the detection of VOCs in living and working environments.
- Metal oxides have broad application prospects in the field of gas detection due to their excellent gas response characteristics. However, its poor sensitivity and selectivity limit its practical application. It is expected to further improve the performance of materials by constructing nanostructures and heterojunction structures.
- Modification of Co 3 O 4 nanomaterials by Mn 2 O 3 atomic clusters can increase the specific surface area, build more defect states, increase the effective active sites, and improve the sensitivity.
- the thickness of the depletion layer increases the reactivity, thereby improving the sensitivity to the target gas and realizing highly sensitive detection of the target gas.
- the purpose of the present invention is to provide a simple and feasible preparation method of Mn 2 O 3 atomic cluster modified Co 3 O 4 nanomaterials, and the materials prepared by the method can be used in the fields of gas detection, gas catalysis treatment and the like.
- Another object of the present invention is to provide a packaged IR780@silica product prepared by the above method.
- Another object of the present invention is to provide an application of the above product.
- the object of the present invention is achieved through the following scheme: a preparation method of a manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial for acetone and formaldehyde detection, comprising the following steps:
- Step 1 Take an appropriate amount of cobalt salt, dissolve it in deionized water, the molar concentration of the cobalt salt is 0.01 ⁇ 0.02M, add acetonitrile according to the volume ratio of deionized water and acetonitrile 1 ⁇ 2:1 to obtain a mixed solution, and then molar ratio of cobalt Salt, trimesic acid or 2,5-dihydroxy-1,4-phthalic acid and bipyridine 1:1:1 are dissolved in the above mixed solution, and magnetically stirred for 1-2h;
- Step 2 get manganese salt according to the molar ratio of manganese salt and cobalt salt 5 ⁇ 8:1, dissolve in deionized water, and the concentration of manganese salt is 0.01 ⁇ 0.02M;
- Step 3 Mix the solutions of Steps 1 and 2, stir for 1 to 2 hours, place them in a reaction kettle, perform hydrothermal reaction at 160 to 180° C. for 24 to 36 hours, and then centrifuge to obtain the Co-Mn precursor after the temperature drops to room temperature;
- Step 4 calcining the Co-Mn precursor in a muffle furnace, the calcination temperature is 500-600°C, the heating rate is 1-3°C/min, and the holding time is 4-5h to obtain Co 3 O modified by Mn 2 O 3 atomic clusters 4 nanometer material powder.
- the invention provides a simple preparation method for constructing Mn 2 O 3 atomic clusters to modify Co 3 O 4 nanometer materials, and the preparation process is simple, the preparation cost is low, and the detection of different target gases is realized by using sensitive materials, and the detection of different target gases is realized by using sensitive materials.
- the properties of oxides and advancing semiconductors are extremely valuable for practical applications in acetone and formaldehyde detection.
- the cobalt salt is at least one of cobalt nitrate hexahydrate and cobalt acetate tetrahydrate;
- the manganese salt in step 2 is at least one of manganese nitrate and manganese acetate tetrahydrate.
- the present invention also provides a dimanganese trioxide atomic cluster modified cobalt tetroxide nanomaterial for the detection of acetone and formaldehyde, which is prepared according to any one of the above-mentioned methods.
- the present invention also provides an application of a manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial in preparing a material for acetone and formaldehyde detection.
- the powder prepared by the invention is dispersed and coated on the gas-sensing test element of the hexapod ceramic tube, and the sensitivity to acetone and formaldehyde gas is tested. -85.6; the best response temperature to formaldehyde gas is 180°C, and the response sensitivity to formaldehyde gas with a concentration of 100ppm is 79.4-87.3.
- the invention discloses a preparation method of manganese trioxide atomic cluster modified cobalt tetroxide used for the detection of acetone and formaldehyde.
- the invention takes an aqueous cobalt salt solution, mixes it with acetonitrile, and then adds trimesic acid or 2,5-dihydroxy- 1,4-phthalic acid and bipyridine are mixed with an aqueous solution of manganese salt after magnetic stirring, and the Co-Mn precursor is obtained after hydrothermal reaction, and then calcined at high temperature in a muffle furnace to obtain Mn 2 O 3 atoms Cluster - modified Co3O4 nanomaterials.
- the product obtained by the invention regulates the surface and bulk defects of the material, and at the same time comprehensively utilizes the adsorption and catalysis properties of the two to gas, so as to realize the detection of acetone and formaldehyde gas by using the same sensitive material.
- Figure 1 shows the sensitivity of the Co 3 O 4 nanomaterials modified with the Mn 2 O 3 atomic clusters of the present invention to different gases at a working temperature of 150°C; The response sensitivity is significantly better than other gases;
- Figure 2 shows the sensitivity of the Co 3 O 4 nanomaterials modified by the Mn 2 O 3 atomic clusters of the present invention to different gases at a working temperature of 180°C.
- the response sensitivity is significantly better than other gases.
- the invention can use the same material to have different optimal corresponding temperatures for different target gases, and use this property of the material to realize the detection of different target gases through programming in the device preparation process.
- a manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial for acetone and formaldehyde detection is prepared according to the following steps:
- Step 1 take an appropriate amount of 0.1 mmol of cobalt nitrate hexahydrate, dissolve in 10 mL of deionized water, and then add 10 mL of acetonitrile to obtain a mixed solution; then, take 0.1 mmol of trimesic acid and 0.1 mmol of bipyridine and dissolve in the above mixed solution medium, magnetic stirring for 1-2 h;
- Step 2 take 0.5mmol of manganese nitrate and dissolve it in 50mL of deionized water;
- step 3 the solutions of steps 1 and 2 are mixed, stirred for 1-2 hours, placed in a reaction kettle, and subjected to a hydrothermal reaction at 160° C. for 36 hours. After the temperature is lowered to room temperature, the Co-Mn precursor is obtained by centrifugation;
- the Co-Mn precursor is calcined in a muffle furnace, calcined at 500° C. for 5 hours, and the heating rate is 1° C./min to obtain a Co 3 O 4 nanomaterial decorated with powdery Mn 2 O 3 atomic clusters.
- the dispersion prepared in this example is applied to the gas sensing test element of the hexapod ceramic tube, and the sensitivity to acetone and formaldehyde gas is tested.
- the optimum response temperature to acetone gas is 150°C, and the response sensitivity to acetone gas with a concentration of 100 ppm is 83.2;
- the optimal response temperature to formaldehyde gas is 180°C, and the response sensitivity to formaldehyde gas with a concentration of 100ppm is 84.1.
- a manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial used for the detection of acetone and formaldehyde which is similar to the steps of Example 1, and prepared according to the following steps:
- Step 1 take an appropriate amount of 0.15mmol of cobalt nitrate hexahydrate, dissolve it in 10mL of deionized water, then add 10mL of acetonitrile to obtain a mixed solution, then take 0.15mmol of trimesic acid and 0.15mmol of bipyridine to dissolve in the above mixed solution , magnetic stirring for 1 ⁇ 2h;
- Step 2 take 0.9 mmol of manganese nitrate and dissolve it in 90 mL of deionized water;
- Step 3 After stirring for 2 hours, place it in a reaction kettle, conduct hydrothermal reaction at 180°C for 36 hours, and after the temperature drops to room temperature, centrifuge to obtain the Co-Mn precursor;
- the Co-Mn precursor is calcined in a muffle furnace, calcined at 600° C. for 5 hours, and the heating rate is 3° C./min to obtain a Co 3 O 4 nanomaterial decorated with powdery Mn 2 O 3 atomic clusters.
- the powder prepared in this example is dispersed and coated on the gas-sensing test element of the hexapod ceramic tube, and the sensitivity to acetone and formaldehyde gas is tested. 85.6; the best response temperature to formaldehyde gas is 180°C, and the response sensitivity to formaldehyde gas with a concentration of 100ppm is 79.4.
- a manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial used for the detection of acetone and formaldehyde which is similar to the steps of Example 1, and prepared according to the following steps:
- Step 1 take an appropriate amount of 0.1 mmol of cobalt nitrate hexahydrate, dissolve in 8 mL of deionized water, then add 8 mL of acetonitrile to obtain a mixed solution, then take 0.1 mmol of trimesic acid and 0.1 mmol of bipyridine to dissolve in the above mixed solution , magnetic stirring for 1 ⁇ 2h;
- Step 1 take 0.8mmol of manganese nitrate and dissolve it in 60mL of deionized water;
- Step 3 After stirring for 2 hours, place it in a reaction kettle, conduct hydrothermal reaction at 180°C for 36 hours, and after the temperature drops to room temperature, centrifuge to obtain the Co-Mn precursor;
- the Co-Mn precursor is calcined in a muffle furnace, calcined at 600° C. for 5 hours, and the heating rate is 3° C./min to obtain a Co 3 O 4 nanomaterial decorated with powdery Mn 2 O 3 atomic clusters.
- the powder prepared in this example is dispersed and coated on the gas-sensing test element of the hexapod ceramic tube, and the sensitivity to acetone and formaldehyde gas is tested. 81.9; the best response temperature to formaldehyde gas is 180°C, and the response sensitivity to formaldehyde gas with a concentration of 100ppm is 87.3.
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Abstract
Disclosed are a preparation method for a manganese(III) oxide atom cluster modified cobaltosic oxide nano-material for acetone and formaldehyde detection, and a product and application thereof. In the present invention, a cobalt salt aqueous solution is mixed with acetonitrile, then trimesic acid or 2,5-dihydroxy-1,4-phthalic acid and bipyridine are added, and after evenly magnetically stirring, same is mixed with an aqueous solution of manganese salt, a hydrothermal reaction is carried out to then obtain a Co-Mn precursor, and then high-temperature roasting is carried out in a muffle furnace so as to obtain a Mn2O3 atom cluster modified Co3O4 nano-material. The product obtained in the present invention regulates and controls material surface and body defects at the same time as comprehensively utilizing gas adsorption and catalytic characteristics of the two, and achieves the detection of acetone and formaldehyde gas by using the same sensitive material.
Description
本发明涉及一种气敏材料的制备方法，具体是指一种用于检测的三氧化二锰原子簇修饰四氧化三钴纳米纳米材料的制备方法及其产品和应用。尤其用于丙酮和甲醛气体的高灵敏检测。The invention relates to a preparation method of a gas-sensing material, in particular to a preparation method of a dimanganese trioxide atomic cluster modified cobalt tetroxide nanometer material for detection, its product and its application. Especially for highly sensitive detection of acetone and formaldehyde gas.
化工材料常用的可挥发性有机化合物如甲醛、丙酮、甲醇等对人类居住环境造成了严重的污染，长期暴露于有毒气体状态下可使人产生头痛、恶心等症状，严重时甚至引发癌症。因此当务之急是加强对生活和工作环境中VOCs气体的检测。金属氧化物由于具有优异的气体响应特性，在气体检测领域具有广阔的应用前景。然而其灵敏度及选择性差限制了其在实际领域的应用。通过构建纳米结构及异质结结构有望进一步提升材料的性能。Volatile organic compounds commonly used in chemical materials, such as formaldehyde, acetone, methanol, etc., have caused serious pollution to the human living environment. Long-term exposure to toxic gases can cause headaches, nausea and other symptoms, and even cause cancer in severe cases. Therefore, it is imperative to strengthen the detection of VOCs in living and working environments. Metal oxides have broad application prospects in the field of gas detection due to their excellent gas response characteristics. However, its poor sensitivity and selectivity limit its practical application. It is expected to further improve the performance of materials by constructing nanostructures and heterojunction structures.
通过Mn
2O
3原子簇修饰Co
3O
4纳米材料可以增加比表面积，构建更多的缺陷态，可以增加有效活性位点，提升灵敏度，同时掺杂后的复合材料可以构建异质结，增加耗尽层厚度，增加反应活性，进而提升对目标气体的灵敏度，实现对目标气体的高灵敏检测。
Modification of Co 3 O 4 nanomaterials by Mn 2 O 3 atomic clusters can increase the specific surface area, build more defect states, increase the effective active sites, and improve the sensitivity. The thickness of the depletion layer increases the reactivity, thereby improving the sensitivity to the target gas and realizing highly sensitive detection of the target gas.
发明内容SUMMARY OF THE INVENTION
本发明目的在于提供一种简单可行的Mn
2O
3原子簇修饰Co
3O
4纳米材料制备方法，该方法制备的材料可用于气体检测、气体催化治理等领域。
The purpose of the present invention is to provide a simple and feasible preparation method of Mn 2 O 3 atomic cluster modified Co 3 O 4 nanomaterials, and the materials prepared by the method can be used in the fields of gas detection, gas catalysis treatment and the like.
本发明的再一目的在于：提供一种上述方法制备的包裹IR780@硅质体产品。Another object of the present invention is to provide a packaged IR780@silica product prepared by the above method.
本发明的又一目的在于：提供一种上述产品的应用。Another object of the present invention is to provide an application of the above product.
本发明目的通过下述方案实现：一种用于丙酮和甲醛检测的三氧化二锰原子簇修饰四氧化三钴纳米材料的制备方法，包括如下步骤：The object of the present invention is achieved through the following scheme: a preparation method of a manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial for acetone and formaldehyde detection, comprising the following steps:
步骤一：取适量钴盐，溶于去离子水，钴盐的摩尔浓度为0.01～0.02M，按去离子水和乙腈体积比1～2：1加入乙腈，得到混合溶液，然后按摩尔比钴盐、均苯三甲酸或2,5-二羟基-1,4-苯二甲酸和联二吡啶1：1：1溶于上述混合溶液中，磁力搅拌1～2h；Step 1: Take an appropriate amount of cobalt salt, dissolve it in deionized water, the molar concentration of the cobalt salt is 0.01~0.02M, add acetonitrile according to the volume ratio of deionized water and acetonitrile 1~2:1 to obtain a mixed solution, and then molar ratio of cobalt Salt, trimesic acid or 2,5-dihydroxy-1,4-phthalic acid and bipyridine 1:1:1 are dissolved in the above mixed solution, and magnetically stirred for 1-2h;
步骤二：按锰盐和钴盐摩尔比取5～8：1取锰盐，溶于去离子水中，锰盐浓度为0.01～0.02M；Step 2: get manganese salt according to the molar ratio of manganese salt and cobalt salt 5～8:1, dissolve in deionized water, and the concentration of manganese salt is 0.01～0.02M;
步骤三：将步骤一、二溶液混合，搅拌1～2h后，置于反应釜中，160～180℃ 水热反应24～36h，待温度降至室温，离心得到Co-Mn前驱体；Step 3: Mix the solutions of Steps 1 and 2, stir for 1 to 2 hours, place them in a reaction kettle, perform hydrothermal reaction at 160 to 180° C. for 24 to 36 hours, and then centrifuge to obtain the Co-Mn precursor after the temperature drops to room temperature;
步骤四：将Co-Mn前驱体于马弗炉下焙烧，焙烧温度500～600℃，升温速度1～3℃/min，保温时间4～5h，得到Mn
2O
3原子簇修饰的Co
3O
4纳米材料粉体。
Step 4: calcining the Co-Mn precursor in a muffle furnace, the calcination temperature is 500-600°C, the heating rate is 1-3°C/min, and the holding time is 4-5h to obtain Co 3 O modified by Mn 2 O 3 atomic clusters 4 nanometer material powder.
本发明提供了一种简单的构建Mn
2O
3原子簇修饰Co
3O
4纳米材料的制备方法，且制备工艺简单，制备成本低，且利用敏感材料实现对不同目标气体的检测，对提升金属氧化物的性能和推进半导体在丙酮和甲醛检测的实际应用领域极具价值。
The invention provides a simple preparation method for constructing Mn 2 O 3 atomic clusters to modify Co 3 O 4 nanometer materials, and the preparation process is simple, the preparation cost is low, and the detection of different target gases is realized by using sensitive materials, and the detection of different target gases is realized by using sensitive materials. The properties of oxides and advancing semiconductors are extremely valuable for practical applications in acetone and formaldehyde detection.
步骤一中，所述的钴盐为六水合硝酸钴，四水合乙酸钴中的至少一种；步骤二所说的锰盐为硝酸锰、四水合乙酸锰的至少一种。In step 1, the cobalt salt is at least one of cobalt nitrate hexahydrate and cobalt acetate tetrahydrate; the manganese salt in step 2 is at least one of manganese nitrate and manganese acetate tetrahydrate.
本发明还提供了一种用于丙酮和甲醛检测的三氧化二锰原子簇修饰四氧化三钴纳米材料，根据上述任一所述方法制备得到。The present invention also provides a dimanganese trioxide atomic cluster modified cobalt tetroxide nanomaterial for the detection of acetone and formaldehyde, which is prepared according to any one of the above-mentioned methods.
本发明也提供了一种三氧化二锰原子簇修饰四氧化三钴纳米材料在制备用于丙酮和甲醛检测材料中的应用。The present invention also provides an application of a manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial in preparing a material for acetone and formaldehyde detection.
本发明制得的粉体分散涂于六脚陶瓷管气敏测试元件上，测试对丙酮和甲醛气体的灵敏度，对丙酮气体最佳响应温度为150℃，对浓度100ppm的丙酮气体响应灵敏度为81.9-85.6；对甲醛气体最佳响应温度为180℃，对浓度100ppm的甲醛气体响应灵敏度为79.4-87.3。The powder prepared by the invention is dispersed and coated on the gas-sensing test element of the hexapod ceramic tube, and the sensitivity to acetone and formaldehyde gas is tested. -85.6; the best response temperature to formaldehyde gas is 180℃, and the response sensitivity to formaldehyde gas with a concentration of 100ppm is 79.4-87.3.
本发明公开了一种用于丙酮和甲醛检测的三氧化二锰原子簇修饰四氧化三钴的制备方法，本发明取钴盐水溶液，与乙腈混合，然后加入均苯三甲酸或2,5-二羟基-1,4-苯二甲酸和联二吡啶，磁力搅拌均匀后，与锰盐的水溶液混合，水热反应后得到Co-Mn前驱体，然后在马弗炉中高温焙烧，得到Mn
2O
3原子簇修饰Co
3O
4纳米材料。本发明所得产品调控材料表面和体缺陷的同时，综合利用二者对气体的吸附和催化特性，实现利用同一种敏感材料对丙酮和甲醛气体的检测。
The invention discloses a preparation method of manganese trioxide atomic cluster modified cobalt tetroxide used for the detection of acetone and formaldehyde. The invention takes an aqueous cobalt salt solution, mixes it with acetonitrile, and then adds trimesic acid or 2,5-dihydroxy- 1,4-phthalic acid and bipyridine are mixed with an aqueous solution of manganese salt after magnetic stirring, and the Co-Mn precursor is obtained after hydrothermal reaction, and then calcined at high temperature in a muffle furnace to obtain Mn 2 O 3 atoms Cluster - modified Co3O4 nanomaterials. The product obtained by the invention regulates the surface and bulk defects of the material, and at the same time comprehensively utilizes the adsorption and catalysis properties of the two to gas, so as to realize the detection of acetone and formaldehyde gas by using the same sensitive material.
图1为以本发明的Mn
2O
3原子簇修饰Co
3O
4纳米材料在工作温度150℃状态下对不同气体的灵敏度；由图1可以看出，在工作温度150℃时，样品对丙酮的响应灵敏度明显优于其他气体；
Figure 1 shows the sensitivity of the Co 3 O 4 nanomaterials modified with the Mn 2 O 3 atomic clusters of the present invention to different gases at a working temperature of 150°C; The response sensitivity is significantly better than other gases;
图2为以本发明的Mn
2O
3原子簇修饰Co
3O
4纳米材料在工作温度180℃状态下对不同气体的灵敏度,由图2可以看出，在工作温度180℃时，样品对甲醛的响应灵敏度明显优于其他气体。
Figure 2 shows the sensitivity of the Co 3 O 4 nanomaterials modified by the Mn 2 O 3 atomic clusters of the present invention to different gases at a working temperature of 180°C. The response sensitivity is significantly better than other gases.
本发明可以利用同一种材料对不同目标气体最佳相应温度不同，利用材料的这一属性可以通过器件制备过程中利用编程的形式实现对不同目标气体的检测。The invention can use the same material to have different optimal corresponding temperatures for different target gases, and use this property of the material to realize the detection of different target gases through programming in the device preparation process.
实施例1：Example 1:
一种用于丙酮和甲醛检测的三氧化二锰原子簇修饰四氧化三钴纳米材料，按如下步骤制备：A manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial for acetone and formaldehyde detection is prepared according to the following steps:
步骤一，取适量0.1mmol六水合硝酸钴，溶于10mL去离子水，然后加入10mL乙腈，得到混合溶液；然后，取0.1mmol的均苯三甲酸和0.1mmol的联二吡啶溶于上述混合溶液中，磁力搅拌1～2h；Step 1, take an appropriate amount of 0.1 mmol of cobalt nitrate hexahydrate, dissolve in 10 mL of deionized water, and then add 10 mL of acetonitrile to obtain a mixed solution; then, take 0.1 mmol of trimesic acid and 0.1 mmol of bipyridine and dissolve in the above mixed solution medium, magnetic stirring for 1-2 h;
步骤二，取0.5mmol的硝酸锰，溶于50mL去离子水中； Step 2, take 0.5mmol of manganese nitrate and dissolve it in 50mL of deionized water;
步骤三，步骤一和二的溶液混合，搅拌1～2h后，置于反应釜中，160℃水热反应36h，待温度降至室温，离心得到Co-Mn前驱体；In step 3, the solutions of steps 1 and 2 are mixed, stirred for 1-2 hours, placed in a reaction kettle, and subjected to a hydrothermal reaction at 160° C. for 36 hours. After the temperature is lowered to room temperature, the Co-Mn precursor is obtained by centrifugation;
步骤四，将Co-Mn前驱体于马弗炉下焙烧，500℃焙烧5h，升温速度1℃/min，得到粉体状的Mn
2O
3原子簇修饰的Co
3O
4纳米材料。
In the fourth step, the Co-Mn precursor is calcined in a muffle furnace, calcined at 500° C. for 5 hours, and the heating rate is 1° C./min to obtain a Co 3 O 4 nanomaterial decorated with powdery Mn 2 O 3 atomic clusters.
本实施例制得的分散涂于六脚陶瓷管气敏测试元件上，测试对丙酮和甲醛气体的灵敏度，对丙酮气体最佳响应温度为150℃，对浓度100ppm的丙酮气体响应灵敏度为83.2；对甲醛气体最佳响应温度为180℃，对浓度100ppm的甲醛气体响应灵敏度为84.1。The dispersion prepared in this example is applied to the gas sensing test element of the hexapod ceramic tube, and the sensitivity to acetone and formaldehyde gas is tested. The optimum response temperature to acetone gas is 150°C, and the response sensitivity to acetone gas with a concentration of 100 ppm is 83.2; The optimal response temperature to formaldehyde gas is 180℃, and the response sensitivity to formaldehyde gas with a concentration of 100ppm is 84.1.
实施例2：Example 2:
一种用于丙酮和甲醛检测的三氧化二锰原子簇修饰四氧化三钴纳米材料，与实施例1步骤相近，按如下步骤制备：A manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial used for the detection of acetone and formaldehyde, which is similar to the steps of Example 1, and prepared according to the following steps:
步骤一，取适量0.15mmol六水合硝酸钴，溶于10mL去离子水，然后加入10mL乙腈，得到混合溶液，然后取0.15mmol的均苯三甲酸和0.15mmol的联二吡啶溶于上述混合溶液中，磁力搅拌1～2h；Step 1, take an appropriate amount of 0.15mmol of cobalt nitrate hexahydrate, dissolve it in 10mL of deionized water, then add 10mL of acetonitrile to obtain a mixed solution, then take 0.15mmol of trimesic acid and 0.15mmol of bipyridine to dissolve in the above mixed solution , magnetic stirring for 1～2h;
步骤二，取0.9mmol的硝酸锰，溶于90mL去离子水中； Step 2, take 0.9 mmol of manganese nitrate and dissolve it in 90 mL of deionized water;
步骤三，搅拌2h后，置于反应釜中，180℃水热反应36h，待温度降至室温，离心得到Co-Mn前驱体；Step 3: After stirring for 2 hours, place it in a reaction kettle, conduct hydrothermal reaction at 180°C for 36 hours, and after the temperature drops to room temperature, centrifuge to obtain the Co-Mn precursor;
步骤四，将Co-Mn前驱体于马弗炉下焙烧，600℃焙烧5h，升温速度3℃/min，得到粉体状的Mn
2O
3原子簇修饰的Co
3O
4纳米材料。
In the fourth step, the Co-Mn precursor is calcined in a muffle furnace, calcined at 600° C. for 5 hours, and the heating rate is 3° C./min to obtain a Co 3 O 4 nanomaterial decorated with powdery Mn 2 O 3 atomic clusters.
本实施例制得的粉体分散涂于六脚陶瓷管气敏测试元件上，测试对丙酮和甲 醛气体的灵敏度，对丙酮气体最佳响应温度为150℃，对浓度100ppm的丙酮气体响应灵敏度为85.6；对甲醛气体最佳响应温度为180℃，对浓度100ppm的甲醛气体响应灵敏度为79.4。The powder prepared in this example is dispersed and coated on the gas-sensing test element of the hexapod ceramic tube, and the sensitivity to acetone and formaldehyde gas is tested. 85.6; the best response temperature to formaldehyde gas is 180℃, and the response sensitivity to formaldehyde gas with a concentration of 100ppm is 79.4.
实施例3：Example 3:
一种用于丙酮和甲醛检测的三氧化二锰原子簇修饰四氧化三钴纳米材料，与实施例1步骤相近，按如下步骤制备：A manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial used for the detection of acetone and formaldehyde, which is similar to the steps of Example 1, and prepared according to the following steps:
步骤一，取适量0.1mmol六水合硝酸钴，溶于8mL去离子水，然后加入8mL乙腈，得到混合溶液，然后取0.1mmol的均苯三甲酸和0.1mmol的联二吡啶溶于上述混合溶液中，磁力搅拌1～2h；Step 1, take an appropriate amount of 0.1 mmol of cobalt nitrate hexahydrate, dissolve in 8 mL of deionized water, then add 8 mL of acetonitrile to obtain a mixed solution, then take 0.1 mmol of trimesic acid and 0.1 mmol of bipyridine to dissolve in the above mixed solution , magnetic stirring for 1～2h;
步骤一，取0.8mmol的硝酸锰，溶于60mL去离子水中；Step 1, take 0.8mmol of manganese nitrate and dissolve it in 60mL of deionized water;
步骤三，搅拌2h后，置于反应釜中，180℃水热反应36h，待温度降至室温，离心得到Co-Mn前驱体；Step 3: After stirring for 2 hours, place it in a reaction kettle, conduct hydrothermal reaction at 180°C for 36 hours, and after the temperature drops to room temperature, centrifuge to obtain the Co-Mn precursor;
步骤四，将Co-Mn前驱体于马弗炉下焙烧，600℃焙烧5h，升温速度3℃/min，得到粉体状的Mn
2O
3原子簇修饰的Co
3O
4纳米材料。
In the fourth step, the Co-Mn precursor is calcined in a muffle furnace, calcined at 600° C. for 5 hours, and the heating rate is 3° C./min to obtain a Co 3 O 4 nanomaterial decorated with powdery Mn 2 O 3 atomic clusters.
本实施例制得的粉体分散涂于六脚陶瓷管气敏测试元件上，测试对丙酮和甲醛气体的灵敏度，对丙酮气体最佳响应温度为150℃，对浓度100ppm的丙酮气体响应灵敏度为81.9；对甲醛气体最佳响应温度为180℃，对浓度100ppm的甲醛气体响应灵敏度为87.3。The powder prepared in this example is dispersed and coated on the gas-sensing test element of the hexapod ceramic tube, and the sensitivity to acetone and formaldehyde gas is tested. 81.9; the best response temperature to formaldehyde gas is 180℃, and the response sensitivity to formaldehyde gas with a concentration of 100ppm is 87.3.
上述的实施例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于这里的实施例，本领域技术人员根据本发明的揭示，对于本发明做出的改进和修改都应该在本发明的保护范围之内。The above-described embodiments are described to facilitate understanding and application of the present invention by those of ordinary skill in the art. It will be apparent to those skilled in the art that various modifications to these embodiments can be readily made, and the generic principles described herein can be applied to other embodiments without inventive step. Therefore, the present invention is not limited to the embodiments herein, and improvements and modifications made to the present invention by those skilled in the art according to the disclosure of the present invention should all fall within the protection scope of the present invention.
Claims (7)
- 一种用于丙酮和甲醛检测的三氧化二锰原子簇修饰四氧化三钴纳米材料的制备方法，其特征在于，包括如下步骤：A preparation method of manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial for acetone and formaldehyde detection, characterized in that, comprising the following steps:步骤一，取适量钴盐，溶于去离子水，制备摩尔浓度为0.01～0.02M的钴盐溶液；按去离子水和乙腈体积比(1～2)：1加入乙腈，得到混合溶液；然后，按摩尔比钴盐、均苯三甲酸或2,5-二羟基-1,4-苯二甲酸和联二吡啶1：1：1溶于上述混合溶液中，磁力搅拌1～2h；Step 1, take an appropriate amount of cobalt salt and dissolve it in deionized water to prepare a cobalt salt solution with a molar concentration of 0.01-0.02M; add acetonitrile according to the volume ratio of deionized water and acetonitrile (1-2): 1 to obtain a mixed solution; then , dissolve cobalt salt, trimesic acid or 2,5-dihydroxy-1,4-phthalic acid and bipyridine 1:1:1 in the above mixed solution in molar ratio, and stir magnetically for 1-2h;步骤二，按锰盐和钴盐摩尔比取(5～8)：1取锰盐，溶于去离子水中制备浓度为0.01～0.02M锰盐溶液；Step 2, according to the molar ratio of manganese salt and cobalt salt (5～8): 1, take manganese salt, dissolve in deionized water to prepare a manganese salt solution with a concentration of 0.01～0.02M;步骤三，步骤一和二的溶液混合，搅拌1～2h后，置于反应釜中，160～180℃水热反应24～36h，待温度降至室温，离心得到Co-Mn前驱体；In step 3, the solutions of steps 1 and 2 are mixed, stirred for 1-2 hours, placed in a reaction kettle, and subjected to a hydrothermal reaction at 160-180° C. for 24-36 hours. After the temperature is lowered to room temperature, the Co-Mn precursor is obtained by centrifugation;步骤四，将Co-Mn前驱体于马弗炉下焙烧，焙烧温度500～600℃，升温速度1～3℃/min，保温时间4～5h，得到Mn 2O 3原子簇修饰的Co 3O 4纳米材料。 In step 4, the Co-Mn precursor is calcined in a muffle furnace, the calcination temperature is 500-600 °C, the heating rate is 1-3 °C/min, and the holding time is 4-5 h to obtain Co 3 O modified by Mn 2 O 3 atomic clusters 4 nanometer materials.
- 根据权利要求1所述用于丙酮和甲醛检测的三氧化二锰原子簇修饰四氧化三钴纳米材料的制备方法，其特征在于：步骤一中，所述的钴盐为六水合硝酸钴，四水合乙酸钴中的至少一种；步骤二中，所述的锰盐为硝酸锰、四水合乙酸锰的至少一种。The preparation method of the manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial for the detection of acetone and formaldehyde according to claim 1, characterized in that: in step 1, the cobalt salt is cobalt nitrate hexahydrate, cobalt acetate tetrahydrate At least one of; in step 2, the manganese salt is at least one of manganese nitrate and manganese acetate tetrahydrate.
- 根据权利要求1或2所述用于丙酮和甲醛检测的三氧化二锰原子簇修饰四氧化三钴纳米材料的制备方法，其特征在于：按如下步骤制备：According to the preparation method of the manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial for acetone and formaldehyde detection according to claim 1 or 2, it is characterized in that: prepare according to the following steps:步骤一，取适量0.1mmol六水合硝酸钴，溶于10mL去离子水，然后加入10mL乙腈，得到混合溶液；然后，取0.1mmol的均苯三甲酸和0.1mmol的联二吡啶溶于上述混合溶液中，磁力搅拌1～2h；Step 1, take an appropriate amount of 0.1 mmol of cobalt nitrate hexahydrate, dissolve in 10 mL of deionized water, and then add 10 mL of acetonitrile to obtain a mixed solution; then, take 0.1 mmol of trimesic acid and 0.1 mmol of bipyridine and dissolve in the above mixed solution medium, magnetic stirring for 1-2 h;步骤二，取0.5mmol的硝酸锰，溶于50mL去离子水中；Step 2, take 0.5mmol of manganese nitrate and dissolve it in 50mL of deionized water;步骤三，步骤一和二的溶液混合，搅拌1～2h后，置于反应釜中，160℃水热反应36h，待温度降至室温，离心得到Co-Mn前驱体；In step 3, the solutions of steps 1 and 2 are mixed, stirred for 1-2 hours, placed in a reaction kettle, and subjected to a hydrothermal reaction at 160° C. for 36 hours. After the temperature is lowered to room temperature, the Co-Mn precursor is obtained by centrifugation;步骤四，将Co-Mn前驱体于马弗炉下焙烧，500℃焙烧5h，升温速度1℃/min，得到粉体状的Mn 2O 3原子簇修饰的Co 3O 4纳米材料。 In the fourth step, the Co-Mn precursor is calcined in a muffle furnace, calcined at 500° C. for 5 hours, and the heating rate is 1° C./min to obtain a Co 3 O 4 nanomaterial decorated with powdery Mn 2 O 3 atomic clusters.
- 根据权利要求1或2所述用于丙酮和甲醛检测的三氧化二锰原子簇修饰四氧化三钴纳米材料的制备方法，其特征在于：按如下步骤制备：According to the preparation method of the manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial for acetone and formaldehyde detection according to claim 1 or 2, it is characterized in that: prepare according to the following steps:步骤一，取适量0.15mmol六水合硝酸钴，溶于10mL去离子水，然后加入 10mL乙腈，得到混合溶液，然后取0.15mmol的均苯三甲酸和0.15mmol的联二吡啶溶于上述混合溶液中，磁力搅拌1～2h；Step 1, take an appropriate amount of 0.15mmol of cobalt nitrate hexahydrate, dissolve it in 10mL of deionized water, then add 10mL of acetonitrile to obtain a mixed solution, then take 0.15mmol of trimesic acid and 0.15mmol of bipyridine to dissolve in the above mixed solution , magnetic stirring for 1～2h;步骤二，取0.9mmol的硝酸锰，溶于90mL去离子水中；Step 2, take 0.9 mmol of manganese nitrate and dissolve it in 90 mL of deionized water;步骤三，搅拌2h后，置于反应釜中，180℃水热反应36h，待温度降至室温，离心得到Co-Mn前驱体；Step 3: After stirring for 2 hours, place it in a reaction kettle, conduct hydrothermal reaction at 180°C for 36 hours, and after the temperature drops to room temperature, centrifuge to obtain the Co-Mn precursor;步骤四，将Co-Mn前驱体于马弗炉下焙烧，600℃焙烧5h，升温速度3℃/min，得到粉体状的Mn 2O 3原子簇修饰的Co 3O 4纳米材料。 In the fourth step, the Co-Mn precursor is calcined in a muffle furnace, calcined at 600° C. for 5 hours, and the heating rate is 3° C./min to obtain a Co 3 O 4 nanomaterial decorated with powdery Mn 2 O 3 atomic clusters.
- 根据权利要求1或2所述用于丙酮和甲醛检测的三氧化二锰原子簇修饰四氧化三钴纳米材料的制备方法，其特征在于：按如下步骤制备：According to the preparation method of the manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial for acetone and formaldehyde detection according to claim 1 or 2, it is characterized in that: prepare according to the following steps:步骤一，取适量0.1mmol六水合硝酸钴，溶于8mL去离子水，然后加入8mL乙腈，得到混合溶液，然后取0.1mmol的均苯三甲酸和0.1mmol的联二吡啶溶于上述混合溶液中，磁力搅拌1～2h；Step 1, take an appropriate amount of 0.1 mmol of cobalt nitrate hexahydrate, dissolve in 8 mL of deionized water, then add 8 mL of acetonitrile to obtain a mixed solution, then take 0.1 mmol of trimesic acid and 0.1 mmol of bipyridine to dissolve in the above mixed solution , magnetic stirring for 1～2h;步骤一，取0.8mmol的硝酸锰，溶于60mL去离子水中；Step 1, take 0.8mmol of manganese nitrate and dissolve it in 60mL of deionized water;步骤三，搅拌2h后，置于反应釜中，180℃水热反应36h，待温度降至室温，离心得到Co-Mn前驱体；Step 3: After stirring for 2 hours, place it in a reaction kettle, conduct hydrothermal reaction at 180°C for 36 hours, and after the temperature drops to room temperature, centrifuge to obtain the Co-Mn precursor;步骤四，将Co-Mn前驱体于马弗炉下焙烧，600℃焙烧5h，升温速度3℃/min，得到粉体状的Mn 2O 3原子簇修饰的Co 3O 4纳米材料。 In the fourth step, the Co-Mn precursor is calcined in a muffle furnace, calcined at 600° C. for 5 hours, and the heating rate is 3° C./min to obtain a Co 3 O 4 nanomaterial decorated with powdery Mn 2 O 3 atomic clusters.
- 一种用于丙酮和甲醛检测的三氧化二锰原子簇修饰四氧化三钴纳米材料，其特征在于根据权利要求1-5任一所述方法制备得到。A manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial for acetone and formaldehyde detection is characterized in that it is prepared according to any one of claims 1-5.
- 一种根据权利要求6所述三氧化二锰原子簇修饰四氧化三钴纳米材料在制备用于丙酮和甲醛检测材料中的应用。An application of the manganese trioxide atomic cluster modified cobalt tetroxide nanomaterial according to claim 6 in preparing a material for acetone and formaldehyde detection.
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