CN113198498A - FePO4-MoOXPreparation method of-graphene aerogel catalyst material - Google Patents
FePO4-MoOXPreparation method of-graphene aerogel catalyst material Download PDFInfo
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- CN113198498A CN113198498A CN202110456844.7A CN202110456844A CN113198498A CN 113198498 A CN113198498 A CN 113198498A CN 202110456844 A CN202110456844 A CN 202110456844A CN 113198498 A CN113198498 A CN 113198498A
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 89
- 239000004964 aerogel Substances 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 80
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 36
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 25
- 229910015711 MoOx Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 22
- 239000000017 hydrogel Substances 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 9
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 230000002431 foraging effect Effects 0.000 claims description 2
- XNCMOUSLNOHBKY-UHFFFAOYSA-H iron(3+);trisulfate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XNCMOUSLNOHBKY-UHFFFAOYSA-H 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000013335 mesoporous material Substances 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to FePO4‑MoOxPreparation method of graphene aerogel catalyst material based on graphene aerogel with high porosity, large specific surface area, high electron mobility, catalytic active sites and mesoporous material FePO4Nano-aggregate and crystalline MoOxHas the advantages of higher activity and the like in the field of catalysis, and FePO with excellent catalytic performance is prepared by a sol-gel process and a hydrothermal reduction method4‑MoOx-a graphene aerogel catalyst material. Wherein, FePO4And MoOxProvides catalytic activity and selectivity for the composite material, and is loaded on graphene aerogelThe conversion of methane is promoted. Prepared FePO4‑MoOxThe specific surface area of the graphene aerogel catalyst material is 122.4-368.3 g/cm370ml/min of CH at a temperature of 200-650 DEG C4/O2Under the mixed flow rate of 32/4.3/63.7/He, the conversion rate of methane reaches 3.26-4.85%, and the selectivity of formaldehyde reaches 10.2-17.1%.
Description
Technical Field
The invention belongs to the field of preparation technology of nano porous materials, and relates to FePO with low density, high specific surface area and catalytic activity4-MoOx-a method for preparing a graphene aerogel catalyst material.
Background
Natural gas plays an important role in energy structures, and is expected to replace petroleum and coal to become a main chemical and energy raw material in the long term and sustainable development. The conversion and application of methane as a main component of natural gas are important research directions in the chemical field of natural gas, and the conversion of methane is always a focus and key point of research because methane is difficult to transport. The selection of a suitable catalyst material is critical to the catalysis of methane.
Extensive studies have demonstrated the presence of an excess of crystalline MoO on the surface of the catalystxCan improve the catalytic performance of the selective oxidation reaction of the methanol and introduce a mesoporous material FePO4Nano aggregate pair CH4The selective oxidation performance plays a great role. However, the powder material has aggregation problem, so that the utilization rate of the catalyst material is low. Graphene has high mechanical strength, a large theoretical specific surface area, a large number of functional groups and active sites on the surface and good hydrophobicity, the three-dimensional graphene aerogel inherits the excellent performance of graphene and aerogel, and the surface has a plurality of catalytic active sites, so that the graphene aerogel is widely noticed in the field of catalysis.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides FePO4-MoOx-a method for preparing a graphene aerogel catalyst material.
The technical scheme of the invention is as follows: graphene aerogel based on high porosity, large specific surface area, high electron mobility, catalytic active sites and mesoporous material FePO4Nano-aggregate and crystalline MoOxHas the advantages of higher activity and the like in the field of catalysis, and FePO with excellent catalytic performance is prepared by a sol-gel process and a hydrothermal reduction method4-MoOx-a graphene aerogel catalyst material. FePO is reacted with4With MoOxThe catalyst is compounded with graphene aerogel, so that the catalyst not only has active components capable of improving catalytic activity, but also has high specific surface area and can enable the catalyst material to efficiently play a role. The load of the active component improves the agglomeration among graphene sheet layers, and the graphene aerogel is used as a carrier, so that more catalytic active sites are provided for the active component, the dispersity of the active oxide nanoparticles is improved, and the active component can be more fully contacted with reactants.
The specific technical scheme of the invention is as follows: FePO4-MoOxPreparation method of-graphene aerogel catalyst material and prepared FePO4-MoOxThe specific surface area of the graphene aerogel catalyst material is 122.4-368.3 g/cm370ml/min of CH at a temperature of 200-650 DEG C4/O2Under the mixing flow rate of 32/4.3/63.7 (volume ratio) of/He, the conversion rate of methane reaches 3.26-4.85%, and the selectivity of formaldehyde reaches 10.2-17.1%. The method comprises the following specific steps:
(1) dispersing ferric salt and ammonium dihydrogen phosphate in deionized water during stirring, uniformly stirring to obtain a mixed solution, heating and stirring the mixed solution until powder is obtained, and drying the powder in an oven to obtain FePO4；
(2) Uniformly dispersing graphene oxide GO in deionized water during stirring, and uniformly stirring at room temperature to obtain a graphene oxide aqueous solution;
(3) FePO is reacted with4Dissolving the powder in deionized water, and stirring at room temperature for a period of time to obtain FePO4A suspension;
(4) mixing graphene oxide aqueous solution with FePO4Mixing the suspension, adding ammonium molybdate tetrahydrate, stirring at room temperature for a period of time, and performing ultrasonic dispersion to obtain a mixed dispersion liquid;
(5) pouring the dispersion liquid obtained in the step (4) into a liner of a hydrothermal reaction kettle, and carrying out hydrothermal reaction to obtain FePO4-MoOx-a graphene hydrogel;
(6) FePO in the step (5)4-MoOx-taking out the graphene hydrogel from the furnace, putting the graphene hydrogel into deionized water for aging, and replacing the deionized water once at intervals to replace the solvent;
(7) taking out the sample replaced by the solution in the step (6), and freeze-drying to obtain FePO4-MoOx-a graphene aerogel catalyst material.
Preferably, the ferric salt in the step (1) is ferric nitrate nonahydrate or ferric sulfate heptahydrate; fe: the molar ratio of P is 1: (0.5 to 3); the heating and stirring temperature is 70-90 ℃; the drying temperature is 50-90 ℃, and the drying time is 12-48 h.
Preferably, the concentration of the graphene oxide in the graphene oxide aqueous solution in the step (2) is 4-8 mg/ml.
Preferably, FePO is added in the step (3)4The concentration of the suspension is 2-8 times of that of the graphene oxide aqueous solution; the stirring time is 20-60 min.
Preferably, the graphene oxide aqueous solution and FePO in the step (4)4The volume ratio of the suspension is 0.5-3; the addition amount of ammonium molybdate tetrahydrate is Mo: the molar ratio of Fe is 0.5-3; stirring for 20-60 min; the ultrasonic frequency is 80-120 kHz, and the time is 20-50 min.
Preferably, the temperature of the hydrothermal reaction in the step (5) is 160-190 ℃, and the time of the hydrothermal reaction is 11-15 h.
Preferably, the aging time in the step (6) is 4-8 h; the solvent replacement interval time is 10-14 h, and the replacement times are 4-8.
Preferably, the temperature of the freeze drying in the step (7) is-50 to-60 ℃, and the time of the freeze drying is 24 to 48 hours.
FePO prepared by the invention4-MoOxThe specific surface area of the graphene aerogel catalyst material is 122.4-368.3 g/cm370ml/min of CH at a temperature of 200-650 DEG C4/O2Under the mixing flow rate of 32/4.3/63.7 (volume ratio) of/He, the conversion rate of methane reaches 3.26-4.85%, and the selectivity of formaldehyde reaches 10.2-17.1%.
Has the advantages that:
(1) through sol-gel process, hydrothermal or chemical reduction to prepare FePO material4Nano aggregate, crystalline MoOxThe FePO is compounded with graphene aerogel to prepare FePO with high specific surface area, excellent catalytic performance and excellent selective performance4-MoOx-a graphene aerogel catalyst material.
(2) Wherein, FePO4And MoOxProvides catalytic activity and selectivity for the composite material, and promotes the conversion of methane when being loaded on the graphene aerogel.
(3) The graphene aerogel provides a high specific surface area for the composite material, and avoids the aggregation of active substances to a certain extent, so that the active components are more fully contacted with reactants.
(4) The catalyst material can effectively overcome the defects of single-component materials, thereby greatly improving the catalytic efficiency and the selectivity of target products.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of protection.
Example 1
Ferric nitrate nonahydrate and ammonium dihydrogen phosphate were mixed in a beaker as Fe: the molar ratio of P is 1: 0.5 in the stirring process, dispersing in deionized water, uniformly stirring to obtain a mixed solution, heating and stirring the mixed solution at 70 ℃ until powder is obtained, drying the powder in a 90 ℃ oven for 12 hours to obtain FePO4(ii) a Uniformly dispersing Graphene Oxide (GO) in deionized water in the stirring process, wherein the concentration of the graphene oxide is 4mg/ml, and uniformly stirring at room temperature to obtain a graphene oxide aqueous solution; FePO is reacted with4Dissolving the powder in deionized water, wherein the concentration of the powder is 2 times of that of the graphene oxide aqueous solution, and stirring the solution for 20min at room temperature to obtain FePO4A suspension; mixing graphene oxide aqueous solution with FePO4The suspension was mixed in a volume ratio of 0.5, and Mo: adding ammonium molybdate tetrahydrate according to the molar ratio of Fe of 3, stirring at room temperature for 60min, and ultrasonically dispersing at 80kHz for 50min to obtain a mixed dispersion liquid; pouring the dispersion into the inner container of a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 160 DEG CReacting for 15h to obtain FePO4-MoOx-graphene hydrogel. And after the temperature of the hydrothermal reaction kettle is reduced, taking out the hydrogel from the furnace, aging for 4 hours, putting the hydrogel into deionized water, replacing the deionized water every 10 hours for solvent replacement, and replacing for 8 times. Taking out the replaced sample, freeze-drying at-50 ℃ for 24h, and taking out to obtain FePO4-MoOx-a graphene aerogel catalyst material. Prepared FePO4-MoOx-the specific surface area of the graphene aerogel catalyst material is 122.4g/cm370ml/min CH at 450 ℃4/O2At a mixed flow rate of 32/4.3/63.7 (volume ratio)/He, the methane conversion rate reaches 3.26%, and the formaldehyde selectivity reaches 17.1%.
Example 2
Iron sulfate heptahydrate and ammonium dihydrogen phosphate were mixed in a beaker as a mixture of Fe: the molar ratio of P is 1: 1 in the stirring process, uniformly stirring to obtain a mixed solution, heating and stirring the mixed solution at 75 ℃ until powder is obtained, drying the powder in a 75 ℃ oven for 18 hours to obtain FePO4(ii) a Uniformly dispersing Graphene Oxide (GO) in deionized water in the stirring process, wherein the concentration of the graphene oxide is 5mg/ml, and uniformly stirring at room temperature to obtain a graphene oxide aqueous solution; FePO is reacted with4Dissolving the powder in deionized water, wherein the concentration of the powder is 4 times of that of the graphene oxide aqueous solution, and stirring the solution for 30min at room temperature to obtain FePO4A suspension; mixing graphene oxide aqueous solution with FePO4The suspension was mixed in a volume ratio of 1, and Mo: adding ammonium molybdate tetrahydrate according to the molar ratio of Fe of 2.5, stirring for 50min at room temperature, and ultrasonically dispersing for 40min at 90kHz to obtain a mixed dispersion liquid; pouring the dispersion into the inner container of a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 14h at 165 ℃ to obtain FePO4-MoOx-graphene hydrogel. And after the temperature of the hydrothermal reaction kettle is reduced, taking out the hydrogel from the furnace, aging for 5 hours, putting the hydrogel into deionized water, replacing the deionized water every 11 hours for solvent replacement, and replacing for 7 times. Taking out the replaced sample, freeze-drying at-50 deg.C for 30h, and taking out to obtain FePO4-MoOx-a graphene aerogel catalyst material. Prepared FePO4-MoOxThe specific surface area of the graphene aerogel catalyst material is 243.6g/cm370ml/min CH at 465 DEG C4/O2At a mixed flow rate of 32/4.3/63.7 (volume ratio)/He, the methane conversion rate reaches 3.64%, and the formaldehyde selectivity reaches 16.2%.
Example 3
Ferric nitrate nonahydrate and ammonium dihydrogen phosphate were mixed in a beaker as Fe: the molar ratio of P is 1: 1.5 in the stirring process, dispersing in deionized water, uniformly stirring to obtain a mixed solution, heating and stirring the mixed solution at 80 ℃ until powder is obtained, and drying in a 70 ℃ oven for 24 hours to obtain FePO4(ii) a Uniformly dispersing Graphene Oxide (GO) in deionized water in the stirring process, wherein the concentration of the graphene oxide is 6mg/ml, and uniformly stirring at room temperature to obtain a graphene oxide aqueous solution; FePO is reacted with4Dissolving the powder in deionized water, wherein the concentration of the powder is 6 times of that of the graphene oxide aqueous solution, and stirring the solution at room temperature for 40min to obtain FePO4A suspension; mixing graphene oxide aqueous solution with FePO4The suspension was mixed in a volume ratio of 2, and Mo: adding ammonium molybdate tetrahydrate according to the molar ratio of Fe of 2, stirring at room temperature for 40min, and ultrasonically dispersing at 100kHz for 40min to obtain a mixed dispersion liquid; pouring the dispersion liquid into an inner container of a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 13h at 170 ℃ to obtain FePO4-MoOx-graphene hydrogel. And after the temperature of the hydrothermal reaction kettle is reduced, taking out the hydrogel from the furnace, aging for 6 hours, putting the hydrogel into deionized water, replacing the deionized water every 12 hours for solvent replacement, and replacing for 6 times. Taking out the replaced sample, freeze-drying at-55 deg.C for 36h, and taking out to obtain FePO4-MoOx-a graphene aerogel catalyst material. Prepared FePO4-MoOxThe specific surface area of the graphene aerogel catalyst material is 283.6g/cm370ml/min CH at 470 deg.C4/O2At a mixed flow rate of 32/4.3/63.7 (volume ratio)/He, the methane conversion rate reaches 4.26%, and the formaldehyde selectivity reaches 13.7%.
Example 4
Iron sulfate heptahydrate and ammonium dihydrogen phosphate were mixed in a beaker as a mixture of Fe: the molar ratio of P is 1: 2 in a ratio of stirringDispersing in deionized water, stirring to obtain mixed solution, heating and stirring the mixed solution at 85 ℃ until powder is obtained, drying the powder in an oven at 60 ℃ for 36h to obtain FePO4(ii) a Uniformly dispersing Graphene Oxide (GO) in deionized water in the stirring process, wherein the concentration of the graphene oxide is 7mg/ml, and uniformly stirring at room temperature to obtain a graphene oxide aqueous solution; FePO is reacted with4Dissolving the powder in deionized water, wherein the concentration of the powder is 7 times of that of the graphene oxide aqueous solution, and stirring the solution for 50min at room temperature to obtain FePO4A suspension; mixing graphene oxide aqueous solution with FePO4The suspension was mixed in a volume ratio of 2.5 and the ratio of Mo: adding ammonium molybdate tetrahydrate according to the molar ratio of Fe of 1, stirring at room temperature for 30min, and ultrasonically dispersing at 110kHz for 30min to obtain a mixed dispersion liquid; pouring the dispersion into the inner container of a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12h at 180 ℃ to obtain FePO4-MoOx-graphene hydrogel. And after the temperature of the hydrothermal reaction kettle is reduced, taking out the hydrogel from the furnace, aging for 7 hours, putting the hydrogel into deionized water, replacing the deionized water every 13 hours for solvent replacement, and replacing for 5 times. Taking out the replaced sample, freeze-drying at-55 deg.C for 42h, and taking out to obtain FePO4-MoOx-a graphene aerogel catalyst material. Prepared FePO4-MoOx-specific surface area of graphene aerogel catalyst material of 322.4g/cm370ml/min CH at 475 DEG C4/O2At a mixed flow rate of 32/4.3/63.7 (volume ratio)/He, the methane conversion rate reaches 4.64%, and the formaldehyde selectivity reaches 12.1%.
Example 5
Ferric nitrate nonahydrate and ammonium dihydrogen phosphate were mixed in a beaker as Fe: the molar ratio of P is 1: 3 in the stirring process, uniformly stirring to obtain a mixed solution, heating and stirring the mixed solution at 90 ℃ until powder is obtained, and drying the powder in a 50 ℃ oven for 48 hours to obtain FePO4(ii) a Uniformly dispersing Graphene Oxide (GO) in deionized water in the stirring process, wherein the concentration of the graphene oxide is 8mg/ml, and uniformly stirring at room temperature to obtain a graphene oxide aqueous solution; FePO is reacted with4Dissolving the powder in deionized water to a certain concentrationStirring for 60min at room temperature to obtain FePO, wherein the concentration of the FePO is 8 times of that of the graphene oxide aqueous solution4A suspension; mixing graphene oxide aqueous solution with FePO4The suspension was mixed in a volume ratio of 3, and Mo: adding ammonium molybdate tetrahydrate according to the molar ratio of Fe of 0.5, stirring at room temperature for 20min, and ultrasonically dispersing at 120kHz for 20min to obtain a mixed dispersion liquid; pouring the dispersion into the inner container of a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 11h at 190 ℃ to obtain FePO4-MoOx-graphene hydrogel. And after the temperature of the hydrothermal reaction kettle is reduced, taking out the hydrogel from the furnace, aging for 8 hours, putting the hydrogel into deionized water, replacing the deionized water every 14 hours for solvent replacement, and replacing for 4 times. Taking out the replaced sample, freeze-drying at-60 ℃ for 48h, and taking out to obtain FePO4-MoOx-a graphene aerogel catalyst material. Prepared FePO4-MoOxThe specific surface area of the graphene aerogel catalyst material is 368.3g/cm370ml/min CH at 480 ℃4/O2At a mixed flow rate of 32/4.3/63.7 (volume ratio)/He, the methane conversion rate reaches 4.85%, and the formaldehyde selectivity reaches 10.2%.
Claims (8)
1. FePO4-MoOxPreparation method of-graphene aerogel catalyst material and prepared FePO4-MoOxThe specific surface area of the graphene aerogel catalyst material is 122.4-368.3 g/cm370ml/min of CH at a temperature of 200-650 DEG C4/O2Under the mixing flow rate of 32/4.3/63.7 (volume ratio) of/He, the conversion rate of methane reaches 3.26-4.85%, and the selectivity of formaldehyde reaches 10.2-17.1%. The method comprises the following specific steps:
(1) dispersing ferric salt and ammonium dihydrogen phosphate in deionized water during stirring, uniformly stirring to obtain a mixed solution, heating and stirring the mixed solution until powder is obtained, and drying the powder in an oven to obtain FePO4；
(2) Uniformly dispersing graphene oxide GO in deionized water in the stirring process, and uniformly stirring to obtain a graphene oxide aqueous solution;
(3) FePO is reacted with4The powder is dissolved in deionizationStirring in water for a period of time to obtain FePO4A suspension;
(4) mixing graphene oxide aqueous solution with FePO4Mixing the suspension, adding ammonium molybdate tetrahydrate, stirring for a period of time, and performing ultrasonic dispersion to obtain a mixed dispersion liquid;
(5) pouring the dispersion liquid obtained in the step (4) into a liner of a hydrothermal reaction kettle, and carrying out hydrothermal reaction to obtain FePO4-MoOx-a graphene hydrogel;
(6) FePO in the step (5)4-MoOx-taking out the graphene hydrogel from the furnace, putting the graphene hydrogel into deionized water for aging, and replacing the deionized water once at intervals to replace the solvent;
(7) taking out the sample replaced by the solution in the step (6), and freeze-drying to obtain FePO4-MoOx-a graphene aerogel catalyst material.
2. The method according to claim 1, wherein the ferric salt in step (1) is ferric nitrate nonahydrate or ferric sulfate heptahydrate; fe: the molar ratio of P is 1: (0.5 to 3); the heating and stirring temperature is 70-90 ℃; the drying temperature is 50-90 ℃, and the drying time is 12-48 h.
3. The preparation method according to claim 1, wherein the concentration of graphene oxide in the graphene oxide aqueous solution in the step (2) is 4-8 mg/ml.
4. The process according to claim 1, wherein FePO is added in the step (3)4The concentration of the suspension is 2-8 times of that of the graphene oxide aqueous solution; the stirring time is 20-60 min.
5. The method according to claim 1, wherein the graphene oxide aqueous solution and FePO in the step (4)4The volume ratio of the suspension is 0.5-3; the addition amount of ammonium molybdate tetrahydrate is Mo: the molar ratio of Fe is 0.5-3; stirring for 20-60 min; the ultrasonic frequency is 80-120 kHz, and the time is 20-50 min.
6. The method according to claim 1, wherein the hydrothermal reaction in step (5) is carried out at a temperature of 160 to 190 ℃ for 11 to 15 hours.
7. The method according to claim 1, wherein the aging time in the step (6) is 4 to 8 hours; the solvent replacement interval time is 10-14 h, and the replacement times are 4-8.
8. The method according to claim 1, wherein the temperature of the freeze-drying in the step (7) is-50 to-60 ℃ and the time of the freeze-drying is 24 to 48 hours.
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