CN110280243A - A kind of monatomic noble metal catalyst and its preparation and the application in room temperature catalytic oxidation formaldehyde - Google Patents
A kind of monatomic noble metal catalyst and its preparation and the application in room temperature catalytic oxidation formaldehyde Download PDFInfo
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- CN110280243A CN110280243A CN201910359945.5A CN201910359945A CN110280243A CN 110280243 A CN110280243 A CN 110280243A CN 201910359945 A CN201910359945 A CN 201910359945A CN 110280243 A CN110280243 A CN 110280243A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/45—Gas separation or purification devices adapted for specific applications
- B01D2259/4508—Gas separation or purification devices adapted for specific applications for cleaning air in buildings
Abstract
Present invention relates particularly to a kind of monatomic noble metal catalyst and its preparation and the application in room temperature catalysis formaldehyde, the catalyst is prepared by the following method to obtain: (1) mixing metal oxide with rare earth metal salt solutions, obtain suspension；(2) noble metal precursor liquid solution is mixed with suspension made from step (1), obtains mixed liquor；(3) under ultra-low temperature surroundings, by the mixing in reducing agent solution and step (2), reaction；(4) reactant of step (3) is filtered, washed and is dried, monatomic noble metal catalyst is made.This method is simple and environmentally-friendly, monatomic noble metal catalyst obtained, and atom level dispersion is presented in metal oxide surface in noble metal, and the content of noble metal is low, it is used in the reaction of room temperature catalytic oxidation formaldehyde, shows high Degradation Formaldehyde efficiency, removal rate is 98% or more.
Description
Technical field
The invention belongs to air cleaning application material technical fields, and in particular to a kind of monatomic noble metal catalyst and its
Preparation and the application in room temperature catalytic oxidation formaldehyde.
Background technique
Since 21 century, one of the major issue of room air pollution and health as public attention.Interior decoration material
The use of material, electric equipment products and a variety of household chemicals, causes the degradation of indoor air quality.Formaldehyde is a kind of relatively allusion quotation
The indoor environmental pollution object of type is that one kind is colourless, has special irritant gas, relative molecular mass is 30.03, and relative density is
1.067 soluble easily in water.Influence to human health includes allotriosmia, abnormal pulmonary function, immune system abnormality and nerve center
System exception etc., therefore the content of formaldehyde in interior is reduced directly concerning human health.
Recent domestic reduces indoor formaldehyde content using a variety of Treatment process, mainly include the following types: (1) is adsorbed
Method: porous high-specific surface area material formaldehyde adsorption is utilized, but absorption is easily saturated and need to often replace；(2) low-temperature plasma
Body technique method: being CO by Degradation Formaldehyde using the method release-O and-OH isoreactivity particle of electrion2And H2O, but equipment
Expensive, energy consumption is high, is not suitable for promoting on a large scale；(3) photocatalytic oxidation, TiO2 is most popular photochemical catalyst, at low cost,
Nontoxic and degradation speed is fast, but must can just react under specific light source；(4) catalyst oxidizing process: mainly
On an metal oxide by noble-metal-supported, formaldehyde is converted completely within the effective time.But such catalyst noble metal contains
Amount is higher, and metallic particles particle size is big, is easy to reunite using time long acting component, so as to cause catalyst inactivation.
How in the case where guaranteeing that catalyst degradation formaldehyde efficiency is constant, reduces noble-metal-supported amount and improve catalyst
Noble metal granule is exactly reduced to atomic level by the quantity at superficial catalytic activation center, best conditions, makes noble metal with list
Atomic form high degree of dispersion is supported on carrier surface.
Summary of the invention
Based on the above issues, there is provided a kind of preparation sides of monatomic noble metal catalyst for an object of the present invention
Method, this method is simple and environmentally-friendly, monatomic noble metal catalyst obtained, the metal oxide table that noble metal is modified in rare earth metal
Atom level dispersion is presented in face, and the content of noble metal is low.
To achieve the goals above, technical scheme is as follows:
A kind of preparation method of monatomic noble metal catalyst, includes the following steps:
(1) metal oxide and rare earth metal salt solutions are mixed, obtains suspension；
(2) noble metal precursor liquid solution is mixed with the suspension in step (1), obtains mixed liquor；
(3) under ultra-low temperature surroundings, reducing agent solution is mixed with the mixed liquor in step (2), is reacted；
(4) reactant of step (3) is filtered, washed and is dried, monatomic noble metal catalyst is made.
Preferably, mixing described in step (1) is to carry out under stiring, and the rate of stirring is 100-2000r/min.
Preferably, the concentration of rare earth metal salt solutions described in step (1) is 0.001-0.01mol/L.
Preferably, the concentration of metal oxide is 0.1-1mol/L in suspension described in step (1).
Preferably, rare earth metal salt described in step (1) is LaN3O9·6H2O、CeN3O9·6H2O、H2N3O10In Sc
Any one or more.
Preferably, metal oxide described in step (1) is any one in manganese dioxide or titanium dioxide or two
Kind, wherein the manganese dioxide is preferably meso-porous titanium dioxide manganese nanometer rods, partial size 10-50nm；The titanium dioxide is preferably
The mixing of Detitanium-ore-type and rutile-type, preferably Detitanium-ore-type and rutile-type mass ratio are 8:2-7:3, partial size 5-30nm.
Preferably, mixing described in step (2) is to carry out under stiring, and the rate of stirring is 100-2000r/min.
Preferably, the concentration of noble metal precursor liquid solution described in step (2) is 0.0004-0.01mol/L.
The solvent of noble metal precursor liquid solution described in step (2) is noncondensing anti-freeze solvent under ultra-low temperature surroundings,
Any one or more preferably in water or C1-5 alcohols, more preferably any one in water or ethyl alcohol or two kinds of any ratios
The mixing that the mixing of example, more preferably water and ethyl alcohol are 1:9-1:5 by volume.
Preferably, noble metal precursor body described in step (2) is the chloride and/or nitrate of noble metal, noble metal
Any one or more preferably in Pd, Au, Pt, Ag.
There there is no the quality of rare earth metal salt, noble metal precursor body and metal oxide in mixed liquor described in step (2)
It limits, the content for meeting noble metal in the noble metal for the single atomic dispersion being prepared is 0.1-1wt%.
Preferably, the step (3) specifically comprise the following steps: (3a) under ultra-low temperature surroundings, by reducing agent solution with
Mixed liquor in step (2) cools down 0.5-2h respectively, then remixes stirring, reacts.
Preferably, the step (3) specifically comprise the following steps: (3b1) under ultra-low temperature surroundings, by reducing agent solution with
Suspension in step (1) cools down 0.5-2h respectively, is then again added drop-wise to reducing agent solution in step (1) in suspension, instead
It answers.
Preferably, the step (3) specifically comprise the following steps: (3b2) under ultra-low temperature surroundings, by reducing agent solution with
Suspension in step (1) cools down 0.5-2h respectively, and then reducing agent solution is added drop-wise in the mixed liquor in step (2), drips
After adding, the reaction was continued 2-6h.
Preferably, step (3, (3a), (3b1), in (3b2), the cooling/mixing/dropwise addition/reaction under stiring into
Row, the rate of stirring are 100-2000r/min.
Preferably, step (3b1), in (3b2), the drop speed of reducing agent solution is 0.01-0.1mL/min.
Preferably, the molar ratio of reducing agent described in step (3), (3a), (3b1) and (3b2) and noble metal is 5:1-
100:1；The concentration of reducing agent solution is 0.01-0.1mol/L, avoids reacting violent progress.
The solvent of reducing agent solution described in step (3), (3a), (3b1) and (3b2) is noncondensing under ultra-low temperature surroundings
Any one or more in anti-freeze solvent, preferably water or alcohols, more preferably any one in water or ethyl alcohol or two kinds
The mixing of arbitrary proportion, more preferably water and ethyl alcohol are the mixing of 1:9-1:5 by volume.
Preferably, reducing agent described in step (3), (3a), (3b1) and (3b2) is ascorbic acid, hydrazine hydrate, boron hydrogen
Change any one or more in sodium and potassium borohydride.
Preferably, the solvent of reducing agent solution described in step (3), (3a), (3b1) and (3b2) is pure water and ethyl alcohol
The mixing that mixing, more preferably pure water and ethyl alcohol are 1:9-1:5 by volume.
Preferably, in step (4), filtering and washing described in step (3) carries out under ultralow temperature.
Preferably, in step (4), the temperature of the drying process is 60-100 DEG C, and the time of the drying process is 12-
24h。
Above-mentioned ultralow temperature is -80 to -20 DEG C.
It the second object of the present invention is to provide a kind of monatomic noble metal catalyst, is prepared by the above method
It arrives.
Preferably, the noble metal is dispersed in the metal oxide surface of rare earth metal modification, your gold with monatomic form
The content of category is 0.1-1wt%, in terms of catalyst full dose.
The third object of the present invention is to provide a kind of application of monatomic noble metal catalyst, is by above method system
For what is obtained, can be used in the reaction of room temperature catalytic oxidation formaldehyde.
Beneficial effects of the present invention:
The preparation method of monatomic noble metal catalyst of the invention, this method is simple and environmentally-friendly, and metal oxide has height
Specific surface area and excellent pore-size distribution, precious metal dispersion can be made more preferable, while itself and noble metal interact, enhancing is normal
Warm degradation of formaldehyde effect；The addition of rare earth metal salt can promote dispersibility of the noble metal on carrier, and catalyst can be improved
Anti- poisoning capability；- 80 to -20 DEG C of ultralow reaction temperature can effectively inhibit metal nucleation, to improve monodispersed metal
Atomic concentration；The optimum choice of each raw material and process conditions, the final metal oxide realizing noble metal and being modified in rare earth metal
The atom level on surface is dispersed, and the content of noble metal is 0.1-1wt% in catalyst.The catalyst is used for room temperature catalytic oxidation first
In aldehyde reaction, high Degradation Formaldehyde efficiency is shown at room temperature, removal rate is 98% or more.
Specific embodiment:
Combined with specific embodiments below, the present invention is described in more detail.
A kind of monatomic noble metal catalyst, is prepared by the following method to obtain:
(1) metal oxide and rare earth metal salt solutions are mixed, obtains suspension；
(2) noble metal precursor liquid solution is mixed with the suspension in step (1), obtains mixed liquor；
(3) under ultra-low temperature surroundings, reducing agent solution is mixed with the mixed liquor in step (2), is reacted；
(4) reactant of step (3) is filtered, washed and is dried, monatomic noble metal catalyst is made.
Preferably, mixing described in step (1) is to carry out under stiring, and the rate of stirring is 100-2000r/min, such as
For 100,500,1000,1500,2000r/min.
Preferably, the concentration of rare earth metal salt solutions described in step (1) is 0.001-0.01mol/L；For example,
0.001、0.003、0.006、0.01mol/L。
The solvent of rare earth metal salt solutions described in step (1) is noncondensing anti-freeze solvent under ultra-low temperature surroundings, excellent
It is selected as any one or more in water or C1-5 alcohols, more preferably any one in water or ethyl alcohol or two kinds of arbitrary proportions
Mixing, more preferably water and the ethyl alcohol mixing that is by volume 1:9-1:5, for example, 1:9,1:8,1:7,1:6,1:5.
Preferably, rare earth metal salt described in step (1) is LaN3O9·6H2O、CeN3O9·6H2O、H2N3O10In S
Any one or more.
Preferably, in suspension described in step (1) metal oxide concentration be 0.1-1mol/L, for example, 0.1,
0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1mol/L。
Preferably, metal oxide described in step (1) is any one in manganese dioxide or titanium dioxide or two
Kind, wherein the manganese dioxide is preferably meso-porous titanium dioxide manganese nanometer rods, partial size 10-50nm；The titanium dioxide is preferably
The mixing of Detitanium-ore-type and rutile-type, preferably Detitanium-ore-type and rutile-type mass ratio are 8:2-7:3, partial size 5-30nm.
Preferably, mixing described in step (2) is to carry out under stiring, and the rate of stirring is 100-2000r/min, such as
For 100,500,1000,1500,2000r/min.
Preferably, the concentration of noble metal precursor liquid solution described in step (2) is 0.0001-0.01mol/L, for example,
0.0001、0.0005、0.001、0.005、0.01mol/L。
The solvent of noble metal precursor liquid solution described in step (2) is noncondensing anti-freeze solvent under ultra-low temperature surroundings,
Any one or more preferably in water or C1-5 alcohols, more preferably any one in water or ethyl alcohol or two kinds of any ratios
The mixing that the mixing of example, more preferably water and ethyl alcohol are 1:9-1:5 by volume, for example, 1:9,1:8,1:7,1:6,1:5.
Preferably, noble metal precursor body described in step (2) is the chloride and/or nitrate of noble metal, noble metal
Any one or more preferably in Pd, Au, Pt, Ag.For example, the precious metal salt can be PdCl2、Pd(NO3)2、
Na2PdCl4、HAuCl4﹒ 3H2O、H2PtCl6﹒ 6H2O、Pt(NO3)2、AgNO3In any one or more.
Those skilled in the art knows, selects different noble metal precursor bodies that different noble metals can be prepared and urges
Agent；Noble metal in the noble metal catalyst can be used as single noble metal, also can be used as two or more noble metals.
There there is no the quality of rare earth metal salt, noble metal precursor body and metal oxide in mixed liquor described in step (2)
It limiting, the content for meeting noble metal in the noble metal of single atomic dispersion being prepared is 0.1-1wt%, for example, 0.1,
0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0wt%.
Preferably, the step (3) specifically comprise the following steps: (3a) under ultra-low temperature surroundings, by reducing agent solution with
Mixed liquor in step (2) cools down 0.5-2h respectively, then for example, 0.5,1,1.5,2h remix stirring, reacts.
Preferably, the step (3) specifically comprise the following steps: (3b1) under ultra-low temperature surroundings, by reducing agent solution with
Suspension in step (1) cools down 0.5-2h respectively, then reducing agent solution is added drop-wise to step again by for example, 0.5,1,1.5,2h
Suddenly in (1) in suspension, react.
Preferably, the step (3) specifically comprise the following steps: (3b2) under ultra-low temperature surroundings, by reducing agent solution with
Suspension in step (1) cools down 0.5-2h respectively, then reducing agent solution is added drop-wise to step by for example, 0.5,1,1.5,2h
(2) in the mixed liquor in, after completion of dropwise addition, the reaction was continued 2-6h.
Preferably, step (3, (3a), (3b1), in (3b2), the cooling/mixing/dropwise addition/reaction under stiring into
Row, the rate of stirring are 100-2000r/min, for example, 100,500,1000,1500,2000r/min.
Preferably, step (3b1), in (3b2), the drop speed of reducing agent solution is 0.01-0.1mL/min, for example, 0.01,
0.02、0.03、0.04、0.05、0.06、0.07、0.08、0.09、0.1mL/min。
Preferably, the molar ratio of reducing agent described in step (3), (3a), (3b1) and (3b2) and noble metal is 5:1-
100:1, for example, 5:1,10:1,20:1,50:1,100:1；The concentration of reducing agent solution is 0.01-0.1mol/L, for example,
0.01,0.02,0.03,0.04,0.05,0.06,0.07,0.08,0.09,0.1mol/L, avoid reacting violent progress.
The solvent of reducing agent solution described in step (3), (3a), (3b1) and (3b2) is noncondensing under ultra-low temperature surroundings
Any one or more in anti-freeze solvent, preferably water or alcohols, more preferably any one in water or ethyl alcohol or two kinds
The mixing of arbitrary proportion, more preferably water and ethyl alcohol are the mixing of 1:9-1:5 by volume, for example, 1:9,1:8,1:7,1:6,
1:5。
Preferably, reducing agent described in step (3), (3a), (3b1) and (3b2) is ascorbic acid, hydrazine hydrate, boron hydrogen
Change any one or more in sodium and potassium borohydride.
Preferably, the solvent of reducing agent solution described in step (3), (3a), (3b1) and (3b2) is pure water and ethyl alcohol
The mixing that mixing, more preferably pure water and ethyl alcohol are 1:9-1:5 by volume, for example, 1:9,1:8,1:7,1:6,1:5.
Being filtered, washed and dried treatment process described in step (4), there is no particular limitation, is those skilled in the art
The conventional means and method known.
Preferably, in step (4), filtering and washing described in step (3) carries out under ultralow temperature.
Preferably, in step (4), the temperature of the drying process is 60-100 DEG C, for example, 60,70,80,90,100
DEG C, time of the drying process is 12-24h, for example, 12,15,18,20, for 24 hours.
Above-mentioned ultralow temperature is -80 to -20 DEG C, for example, -80, -70, -60, -50, -40, -30, -20 DEG C.
Monatomic noble metal catalyst made from the above method, noble metal are dispersed in metal oxide table with monatomic form
Face, the content of noble metal are 0.1-1wt%, for example, 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1wt%.
Monatomic noble metal catalyst made from the above method can be used in the reaction of room temperature catalytic oxidation formaldehyde, test environment
Temperature is 25 DEG C, relative humidity 40Rh.It weighs 20g catalyst to be put in 1.5 cubes of standard aldehyde test cabins, using Dongguan ring
Instrument equipment Co., Ltd HY-JQ-1 generator discharges pollution sources formaldehyde, is monitored using Britain recordable type methylene oxide detecting instrument PPM-HTV
Concentration of formaldehyde in cabin, initial concentration 1-2mg/m3, concentration of formaldehyde is reduced to 0.08mg/m in rear deck for 24 hours3Below.
A specific embodiment of the invention is further described below with reference to embodiment, is not therefore limited the present invention
System is among the embodiment described range.
Embodiment 1:
2g meso-porous titanium dioxide manganese nanometer rods are dissolved into 20mL 0.001mol/L LaN3O9·6H2In O solution, match outstanding
Supernatant liquid, solvent are that 1:9 is formed by volume for pure water and ethyl alcohol；Prepare 20mL 0.001mol/LAgNO3Solution, solvent by water and
1:9 is formed ethyl alcohol by volume；Suspension is mixed with silver nitrate solution, mixed liquor is made, prepares 10mL 0.01mol/L boron
Sodium hydride solution, by water and ethyl alcohol, 1:9 is formed solvent by volume；Mixed liquor and reducing agent solution are put in -80 DEG C of low temperature
In reaction chamber, 0.5h, stirring rate 300r/min are stirred；Reducing agent solution is added drop-wise to suspension with the rate of 0.01mL/min
Continue to be stirred to react 2h, stirring rate 300r/min in liquid, after titration；After reaction in -80 DEG C of low temperature environment
Powder obtained is put in 60 DEG C of oven dryings for 24 hours by lower filtering and washing, is obtained the monatomic silver that load capacity is 0.1wt% and is urged
Agent.
Catalyst prepared by embodiment 1 is placed in 1.5 cubes of standard aldehyde test cabins, initial concentration of formaldehyde 1.3mg/
m3, concentration of formaldehyde is 0.07mg/m3 in rear deck for 24 hours.
Embodiment 2:
2g meso-porous titanium dioxide manganese nanometer rods are dissolved into 20mL 0.001mol/L LaN3O9·6H2In O solution, match outstanding
Supernatant liquid, solvent are that 1:9 is formed by volume for pure water and ethyl alcohol；Prepare 20mL 0.01mol/LAgNO3Solution, solvent is by water and second
1:9 is formed alcohol by volume；Suspension is mixed with silver nitrate solution, mixed liquor is made；Prepare 10mL 0.01mol/L boron hydrogen
Change sodium solution, 1:9 is formed solvent by volume by water and ethyl alcohol；The low temperature that mixed liquor and reducing agent solution are put in -80 DEG C is anti-
It answers in case, stirs 0.5h, stirring rate 300r/min；Reducing agent solution is added drop-wise to suspension with the rate of 0.01mL/min
In, continue to be stirred to react 2h, stirring rate 300r/min after titration；After reaction under -80 DEG C of low temperature environment
Powder obtained is put in 60 DEG C of oven dryings for 24 hours by filtering and washing, obtains the monatomic Ag catalyst that load capacity is 1wt%.
Catalyst prepared by embodiment 2 is placed in 1.5 cubes of standard aldehyde test cabins, initial concentration of formaldehyde 1.2mg/
m3, concentration of formaldehyde is 0.03mg/m3 in rear deck for 24 hours.
Embodiment 3:
2g meso-porous titanium dioxide manganese nanometer rods are dissolved into 20mL 0.001mol/L CeN3O9·6H2In O solution, match outstanding
Supernatant liquid, solvent are that 1:9 is formed by volume for pure water and ethyl alcohol；Prepare 20mL 0.01mol/LAgNO3Solution, solvent is by water and second
1:9 is formed alcohol by volume；Suspension is mixed with silver nitrate solution, mixed liquor is made；Prepare 20mL 0.1mol/L hydroboration
Sodium solution, by water and ethyl alcohol, 1:9 is formed solvent by volume；Mixed liquor and reducing agent solution are put in -80 DEG C of low-temp reaction
In case, 0.5h, stirring rate 300r/min are stirred；Reducing agent solution is added drop-wise to suspension with the rate of 0.01mL/min
In, continue to be stirred to react 2h, stirring rate 300r/min after titration；After reaction under -80 DEG C of low temperature environment
Powder obtained is put in 60 DEG C of oven dryings for 24 hours by filtering and washing, obtains the monatomic Ag catalyst that load capacity is 1wt%.
Catalyst prepared by embodiment 3 is placed in 1.5 cubes of standard aldehyde test cabins, initial concentration of formaldehyde 1.4mg/
m3, concentration of formaldehyde is 0.03mg/m3 in rear deck for 24 hours.
Embodiment 4:
2g meso-porous titanium dioxide manganese nanometer rods are dissolved into 20mL 0.001mol/L H2N3O10In Sc solution, match to suspend
Liquid, solvent are that 1:9 is formed by volume for pure water and ethyl alcohol；Prepare 20mL 0.01mol/LAgNO3Solution, solvent is by water and ethyl alcohol
1:9 is formed by volume；Suspension is mixed with silver nitrate solution, mixed liquor is made；Prepare 20mL 0.1mol/L sodium borohydride
Solution, by water and ethyl alcohol, 1:9 is formed solvent by volume；Mixed liquor and reducing agent solution are put in -20 DEG C of low-temp reaction case
In, stir 0.5h, stirring rate 300r/min；Reducing agent solution is added drop-wise in suspension with the rate of 0.01mL/min,
Continue to be stirred to react 2h, stirring rate 300r/min after titration；It is filtered under -20 DEG C of low temperature environment after reaction
Washing, is put in 60 DEG C of oven dryings for 24 hours for powder obtained, obtains the monatomic Ag catalyst that load capacity is 1wt%.
Catalyst prepared by embodiment 4 is placed in 1.5 cubes of standard aldehyde test cabins, initial concentration of formaldehyde 1.2mg/
m3, concentration of formaldehyde is 0.10mg/m3 in rear deck for 24 hours.
Embodiment 5:
2g meso-porous titanium dioxide manganese nanometer rods are dissolved into 20mL0.001mol/L LaN3O9·6H2In O solution, match to suspend
Liquid, solvent are that 1:9 is formed by volume for pure water and ethyl alcohol；Prepare 20mL 0.01mol/LAgNO3Solution, solvent is by water and ethyl alcohol
1:9 is formed by volume；Suspension is mixed with silver nitrate solution, mixed liquor is made；Prepare 10mL 0.01mol/L hydroboration
Sodium solution, by water and ethyl alcohol, 1:9 is formed solvent by volume；Mixed liquor and reducing agent solution are put in -80 DEG C of low-temp reaction
In case, 0.5h, stirring rate 300r/min are stirred；Reducing agent solution is added drop-wise in suspension with the rate of 0.1mL/min,
Continue to be stirred to react 2h, stirring rate 300r/min after titration；It is filtered under -80 DEG C of low temperature environment after reaction
Washing, is put in 60 DEG C of oven dryings for 24 hours for powder obtained, obtains the monatomic Ag catalyst that load capacity is 1wt%.
Catalyst prepared by embodiment 5 is placed in 1.5 cubes of standard aldehyde test cabins, initial concentration of formaldehyde 1.3mg/
m3, concentration of formaldehyde is 0.05mg/m3 in rear deck for 24 hours.
Embodiment 6:
2g titanium dioxide is dissolved into 20mL0.001mol/L LaN3O9·6H2In O solution, with suspension, solvent are
1:9 is formed by volume for pure water and ethyl alcohol；Prepare 20mL 0.01mol/LAgNO3Solution, solvent by water and ethyl alcohol by volume
1:9 composition；Suspension is mixed with silver nitrate solution, mixed liquor is made；10mL 0.01mol/L sodium borohydride solution is prepared, it is molten
By water and ethyl alcohol, 1:9 is formed by volume for agent；Mixed liquor and reducing agent solution are put in -80 DEG C of low-temp reaction case, are stirred
0.5h, stirring rate 300r/min；Reducing agent solution is added drop-wise in suspension with the rate of 0.01mL/min, titration terminates
After continue to be stirred to react 2h, stirring rate 300r/min；The filtering and washing under -80 DEG C of low temperature environment after reaction, will
Powder obtained is put in 60 DEG C of oven dryings for 24 hours, obtains the monatomic Ag catalyst that load capacity is 1wt%.
Catalyst prepared by embodiment 6 is placed in 1.5 cubes of standard aldehyde test cabins, initial concentration of formaldehyde 1.3mg/
m3, concentration of formaldehyde is 0.02mg/m3 in rear deck for 24 hours.
Embodiment 7:
2g meso-porous titanium dioxide manganese nanometer rods are dissolved into 20mL 0.001mol/L LaN3O9·6H2In O solution, match outstanding
Supernatant liquid, solvent are that 1:9 is formed by volume for pure water and ethyl alcohol；Prepare 20mL 0.01mol/LPd (NO3)2Solution, solvent by water and
1:9 is formed ethyl alcohol by volume；Suspension is mixed with palladium nitrate solution, mixed liquor is made；Configure 20mL0.001mol/LPd
(NO3)2Solution, by water and ethyl alcohol, 1:9 is formed solvent by volume；Prepare 10mL 0.01mol/L sodium borohydride solution, solvent by
1:9 is formed by volume for water and ethyl alcohol；Mixed liquor and reducing agent solution are put in -80 DEG C of low-temp reaction case, stir 0.5h,
Stirring rate is 300r/min；Reducing agent solution is added drop-wise in suspension with the rate of 0.01mL/min, after titration after
It is continuous to be stirred to react 2h, stirring rate 300r/min；The filtering and washing under -80 DEG C of low temperature environment after reaction, will be made
Powder be put in 60 DEG C of oven dryings for 24 hours, obtain load capacity be 1wt% monatomic Pd catalyst.
Catalyst prepared by embodiment 7 is placed in 1.5 cubes of standard aldehyde test cabins, initial concentration of formaldehyde 1.2mg/
m3, concentration of formaldehyde is 0.05mg/m3 in rear deck for 24 hours.
Embodiment 8:
4g meso-porous titanium dioxide manganese nanometer rods are dissolved into 20mL 0.001mol/L CeN3O9·6H2In O solution, match outstanding
Supernatant liquid, solvent are that 1:9 is formed by volume for pure water and ethyl alcohol；Configure 20mL 0.01mol/LHAuCl4﹒ 3H2O solution, solvent by
1:9 is formed by volume for water and ethyl alcohol；Suspension is mixed with chlorauric acid solution, mixed liquor is made；Prepare 20mL 0.1mol/L
Sodium borohydride solution, by water and ethyl alcohol, 1:9 is formed solvent by volume；Mixed liquor and reducing agent solution are put in -80 DEG C low
In warm reaction chamber, 0.5h, stirring rate 300r/min are stirred；Reducing agent solution is added drop-wise to the rate of 0.01mL/min outstanding
Continue to be stirred to react 2h, stirring rate 300r/min in supernatant liquid, after titration；After reaction in -80 DEG C of low temperature ring
Powder obtained is put in 60 DEG C of oven dryings for 24 hours by filtering and washing under border, is obtained the monatomic Au that load capacity is 1wt% and is urged
Agent.
Catalyst prepared by embodiment 8 is placed in 1.5 cubes of standard aldehyde test cabins, initial concentration of formaldehyde 1.4mg/
m3, concentration of formaldehyde is 0.03mg/m3 in rear deck for 24 hours.
Embodiment 9:
4g meso-porous titanium dioxide manganese nanometer rods are dissolved into 20mL 0.001mol/L H2N3O10In Sc solution, match to suspend
Liquid, solvent are that 1:9 is formed by volume for pure water and ethyl alcohol；Configure 20mL 0.01mol/LPt (NO3)2Solution, solvent is by water and second
1:9 is formed alcohol by volume；Suspension is mixed with platinum nitrate solution, mixed liquor is made；Prepare 20mL 0.1mol/L hydroboration
Sodium solution, by water and ethyl alcohol, 1:9 is formed solvent by volume；Mixed liquor and reducing agent solution are put in -20 DEG C of low-temp reaction
In case, 0.5h, stirring rate 300r/min are stirred；Reducing agent solution is added drop-wise to suspension with the rate of 0.01mL/min
In, continue to be stirred to react 2h, stirring rate 300r/min after titration；After reaction under -20 DEG C of low temperature environment
Powder obtained is put in 60 DEG C of oven dryings for 24 hours by filtering and washing, obtains the monatomic Pt catalyst that load capacity is 1wt%.
Catalyst prepared by embodiment 9 is placed in 1.5 cubes of standard aldehyde test cabins, initial concentration of formaldehyde 1.2mg/
m3, concentration of formaldehyde is 0.12mg/m3 in rear deck for 24 hours.
The above, preferable specific embodiment only of the invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and invention structure
Think of is subject to equivalent replacement or change, should be covered by the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of monatomic noble metal catalyst, includes the following steps:
(1) metal oxide and rare earth metal salt solutions are mixed, obtains suspension；
(2) noble metal precursor liquid solution is mixed with the suspension in step (1), obtains mixed liquor；
(3) under ultra-low temperature surroundings, reducing agent solution is mixed with the mixed liquor in step (2), is reacted；
(4) reactant of step (3) is filtered, washed and is dried, monatomic noble metal catalyst is made.
2. preparation method according to claim 1, which is characterized in that rare earth metal salt solutions described in step (1)
Concentration is 0.001-0.01mol/L；The concentration of metal oxide is 0.1-1mol/L in the suspension, wherein described dilute
Earth metal salt is any one or more in LaN3O96H2O, CeN3O96H2O, H2N3O10Sc, the metal oxidation
Object is any one or two kinds in manganese dioxide or titanium dioxide.
3. preparation method according to claim 2, which is characterized in that the manganese dioxide is preferably that meso-porous titanium dioxide manganese is received
Rice stick, partial size 10-50nm；The titanium dioxide is preferably the mixing of Detitanium-ore-type and rutile-type, mass ratio 8:2-7:
3, partial size 5-30nm.
4. preparation method according to claim 1, which is characterized in that noble metal precursor liquid solution described in step (2)
Concentration be 0.0001-0.01mol/L；Wherein, the noble metal precursor body is the chloride and/or nitrate of noble metal, expensive
Metal is preferably any one or more in Pd, Au, Pt, Ag.
5. preparation method according to claim 1, which is characterized in that step (3) specifically comprises the following steps: in ultralow temperature
Under environment, it will be mixed in mixed liquor that reducing agent solution is added drop-wise in step (2)；The drop speed of the reducing agent solution is preferably
0.01-0.1mL/min。
6. preparation method according to claim 1, which is characterized in that reducing agent described in step (3) and noble metal
Molar ratio is 5:1-100:1；The concentration of the reducing agent solution is 0.01-0.1mol/L；The reducing agent is Vitamin C
Any one or more in acid, hydrazine hydrate, sodium borohydride and potassium borohydride.
7. preparation method according to claim 1, which is characterized in that the ultralow temperature be -80 to -20 DEG C.
8. a kind of monatomic noble metal catalyst, which is characterized in that the monatomic noble metal catalyst is according to claim
Preparation method described in 1-7 any one is prepared.
9. monatomic noble metal catalyst according to claim 8, which is characterized in that the noble metal is with monatomic form
It is dispersed in the metal oxide surface of rare earth metal modification, the content of noble metal is 0.1-1wt%, in terms of catalyst full dose.
10. the application of monatomic noble metal catalyst according to claim 9 or 10, which is characterized in that described monatomic
Noble metal catalyst is in the reaction of room temperature catalytic oxidation formaldehyde.
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Application publication date: 20190927 |