CN104923232A - Nano mesoporous silica catalyst loaded with nano zero-valent metal and preparation method thereof - Google Patents
Nano mesoporous silica catalyst loaded with nano zero-valent metal and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nano mesoporous silica catalyst loaded with nano zero-valent metal and a preparation method thereof. The nano zero-valent metal is evenly dispersed in nano mesoporous silica materials, the nano zero-valent metal is loaded on the nano mesoporous silica materials by adopting a liquid phase reduction method, and the loading capacity ranges from 10 mg/g to 20 mg/g. According to the nano mesoporous silica catalyst loaded with the nano zero-valent metal and the preparation method thereof, the nano zero-valent metal is loaded on the nano mesoporous silica materials, the dispersity is high, the stability is good, agglomeration and passivation of the zero-valent metal can be avoided, and the activity of the catalyst is kept. The nano mesoporous silica catalyst loaded with the nano zero-valent metal is high in efficiency, low in cost and stable in performance, under the action of the materials of the nano mesoporous silica catalyst loaded with the nano zero-valent metal, target pollutants in a solution are absorbed on the surfaces of the materials firstly, the zero-valent metal in the materials plays a role to reduce the target pollutants, and therefore reduction, degradation and removal of oxidation type pollutants are achieved.
Description
Technical field
The present invention relates to a kind of mesoporous nano Si catalyst of loaded with nano zero-valent metal and the preparation method of this catalyst, belong to water-treatment technology field.
Technical background
The nano material of emerging in large numbers in recent years and grow up and relevant Assembling of Nanoparticles, be all Selective recognition from dimension, space geometry size, band structure, surface characteristic and the reaction mechanism mechanism of reaction etc. of contaminant molecule on material list interface and eliminate hardly degraded organic substance in water and provide most probable, the abundantest selection, this is that traditional environment material can not complete.Wherein zero-valent metal, if Zero-valent Iron, zero-valent nickel, zeroth order zinc etc. are as a kind of excellent electron donor, have cheap and easy to get, safety low-poison, particle diameter is little, specific area is large, reactivity is high and can not produce the advantages such as secondary pollution to environment, becomes the novel pollution control technology received much attention in water pollution control.
At present, nano zero-valence metal all achieves good effect in degraded organic halogen, nitryl aromatic hydrocarbon compound, nitrate nitrogen, perchloric acid, organic dyestuff and heavy metal ion etc.Nano zero valence iron in position application aspect has very large flexibility, can transform pollutant common in multiple environment, reduce its toxicity.These make nano zero-valence metal become a kind of new technology controlling and administer water pollutions.But in actual applications, as nano zero valence iron exists some drawbacks: (1) particle diameter is little, surface energy is large and there is magnetic, easily to reunite, precipitation; (2) reducing activity is very strong, and chemical property is extremely unstable, very easily oxidized after contacting with air, is difficult to keep surface-active for a long time; (3) can ferric hydroxide precipitate be produced when going back parent pollutant, being attached to surface and making its passivation, also can make its phase activity reduction after degradation; (4) easily run off in the reaction, recovery difficult is large, can form potential secondary pollution.Above-mentioned drawback greatly limit the application in practice of nano zero valence iron.Therefore, the difficult point of nano zero-valence metallic reducing technical research concentrates on the reunion suppressing nano particle, the stability improving nano zero-valence metal, keeps the aspects such as activity.
Summary of the invention
For solving the problem, adopting following technique study: by nano zero-valence Metal Supported on other supporters, as orderly mesoporous nano material, reducing oxidation rate, suppressing particle agglomeration, the recycling rate of waterused of particle can also be improved.
The invention provides a kind of mesoporous nano Si catalyst of loaded with nano zero-valent metal, this catalyst activity is high, and specific area is large.
The present invention is achieved through the following technical measures:
A mesoporous nano Si catalyst for loaded with nano zero-valent metal, described nano zero-valence metal adopts liquid phase reduction to load on mesoporous nano silicon materials, and described nano zero-valence metal is dispersed in mesoporous nano silicon materials.
Described nano zero-valence metal is any one in nano zero valence iron, nano zero-valence zinc or nano zero-valence nickel.
Described mesoporous nano silicon materials are any one in SBA-15, MCM-41, MCM-48 or mesoporous nano silicon ball.
The load capacity of described nano zero-valence metal in mesoporous nano silicon is 10 ~ 20mg/g.
Present invention also offers a kind of preparation method of mesoporous nano silicon ball, step is as follows:
(1) by template molecule, 1,3, it is in 10 ~ 15mmol/L NaOH solution that 5-trimethylbenzene is dissolved in concentration, by mixed solution oil bath magnetic agitation 5h under the condition of 80 DEG C, then ethyl orthosilicate is slowly added in mixed solution, then by the condition lower magnetic force stirring 5h of mixed solution at 80 DEG C, isolated by filtration obtains white precipitate, by washed with methanol, dry under 80 DEG C of conditions, obtain particulate;
(2) particulate that step (1) obtains is transferred in isopropyl alcohol and APTES mixed solution, 100 DEG C of continuous heating 5h;
(3) filtering above-mentioned solution, being immersed in 3h in the methyl alcohol/concentrated hydrochloric acid mixed solution of volume ratio 1:100 ~ 1:50 by filtering the material obtained;
(4) dry under centrifugation, vacuum condition, obtain mesoporous nano silicon ball;
In the preparation method of above-mentioned mesoporous nano silicon ball:
The mass/volume g/ml of described template molecule and 1,3,5-trimethylbenzene is than being 1:7;
Described template molecule is 1:500 with the mass/volume g/ml ratio of NaOH solution;
Described template molecule and the mass ratio of ethyl orthosilicate are 1:2 ~ 1:6;
Described template molecule is 1:20 ~ 1:30 with the mass/volume g/ml ratio of isopropyl alcohol;
Described template molecule is 1:50 ~ 1:100 with the mass/volume g/ μ L ratio of APTES;
Described methyl alcohol and the volume ratio of concentrated hydrochloric acid are 1:100 ~ 1:50.
In the preparation method of above-mentioned mesoporous nano silicon ball, described template molecule is any one in softex kw, hexadecyltrimethylammonium chloride, Cetyltrimethylammonium bromide, OTAC, DTAB, DTAC.
Present invention also offers a kind of preparation method of mesoporous nano Si catalyst of loaded with nano zero-valent metal, described nano zero-valence metal adopts liquid phase reduction to load on mesoporous nano silicon materials, and its preparation methods steps is as follows:
(1) take metal soluble-salt according to the load capacity of nano zero-valence metal in mesoporous nano silicon materials, being dissolved in volume ratio is in the ethanol/water mixed solution of 40/60, and adding surfactant and do dispersant, is 6 ~ 7 by 1mol/L NaOH adjust ph;
(2) load capacity according to step (1), adds mesoporous nano silicon materials under mechanical agitation, pass into nitrogen and continue to stir 6h;
(3) be that 0.25 ~ 0.5mol/L reducing agent dropwise joins in the mixed solution of step (2) by concentration, continue in course of reaction to pass into nitrogen, at room temperature react 3h;
(4) carry out being separated after reaction, clean, dry, obtain the mesoporous nano Si catalyst of loaded with nano zero-valent metal.
In above-mentioned preparation method:
The load capacity of nano zero-valence metal in mesoporous nano silicon is 10 ~ 20mg/g;
Metal soluble-salt is 1:100 ~ 1:500 with the mass/volume g/ml ratio of ethanol/water 40/60 mixed solution;
The mass ratio of surfactant and mesoporous nano silicon materials is 1:100 ~ 1:500;
Reducing agent is 200:1 ~ 500:1 with the volume/mass ml/g ratio of metal soluble-salt.
In above-mentioned preparation method, described metal soluble-salt is any one in the soluble chloride of iron, zinc or nickel, nitrate or sulfate.
In above-mentioned preparation method, described surfactant is any one in polyethylene glycol, polyvinylpyrrolidone, Sodium Polyacrylate or polyvinyl alcohol.
In above-mentioned preparation method, described reducing agent is any one in sodium borohydride, potassium borohydride or hydrazine hydrate.
Beneficial effect: the mesoporous nano Si catalyst that the invention provides a kind of loaded with nano zero-valent metal, first the Surface Physical Chemistry character of mesoporous nano silicon materials is utilized, using as the soluble metallic salt adsorption and enrichment of nano zero-valence metallic precursor in material, then under the surfactant of good biocompatibility exists, adopt solution phase chemical reduction to obtain nanoscale zero-valent metal, zero-valent metal decentralization on mesoporous nano silicon materials is high, good stability.
Nano zero-valence Metal Supported on mesoporous nano silicon materials, can be avoided the reunion of zero-valent metal, passivation by the present invention, keeps the activity of catalyst, significantly improves the specific area of catalyst.Catalyst of the present invention is efficient, cheap, stable performance, can quick adsorption pollutant deoxidization, degradation is low toxicity material.
Compared with common zero-valent metal, nanometer nulvalent iron particle of the present invention is in nanoscale, has the features such as specific area is large, high adsorption capacity, surface reaction activity are high, reducing power is strong, more efficiently can remove water oxygen type pollutant.Simultaneously oxidizable for nano zero-valence metal, reunite, the shortcoming of passivation, by nano zero-valence Metal Supported on the mesoporous nano silicon materials that biological safety is good, while avoiding above-mentioned shortcoming, because mesoporous nano silicon materials have, surface area is large, absorption property good, is more conducive to the enrichment of pollutant and accelerates catalytic degradation reaction process.
Detailed description of the invention
Below by specific embodiment, the present invention will be further elaborated, and following embodiment is only to explain the present invention, does not limit its content.
In following embodiment, the material used all can be bought in the market.
Embodiment 1 prepares the mesoporous nano silicon sphere catalyst that load capacity is the loaded with nano Zero-valent Iron of 20mg/g
By 1.0g softex kw, 7.0mL 1,3, it is in 15mmol/L NaOH solution that 5-trimethylbenzene is dissolved in 500mL concentration, by mixed solution oil bath magnetic agitation 5h under the condition of 80 DEG C, then 4g ethyl orthosilicate is slowly added in mixed solution, then by the condition lower magnetic force stirring 5h of mixed solution at 80 DEG C, isolated by filtration obtains white precipitate, by washed with methanol, dry under 80 DEG C of conditions; The particulate obtained is transferred in 20mL isopropyl alcohol and 100 μ L APTES mixed solutions, 100 DEG C of continuous heating 5h; Filtering above-mentioned solution, being immersed in 3h in methyl alcohol/concentrated hydrochloric acid mixed solution that volume ratio is 1:100 by filtering the material obtained, dry under centrifugation, vacuum condition, obtain mesoporous nano silicon ball.
According to load capacity, take 545mg ferrous sulfate, being dissolved in 100mL volume ratio is in the ethanol/water mixed solution of 40/60, add surfactant polyethylene 0.1g and do dispersant, pH is regulated to be 6 ~ 7 with 1mol/L NaOH, add 10g mesoporous nano silicon ball under mechanical agitation, pass into nitrogen and continue to stir 6h; 100mL 0.5mol/L sodium borohydride is dropwise added in mixed solution, and continues to pass into nitrogen in the process of reaction, at room temperature react 3h; Carry out after reaction being separated, clean, dry, obtain the mesoporous nano silicon sphere catalyst that load capacity is the loaded with nano Zero-valent Iron of 20mg/g.
Embodiment 2 prepares the mesoporous nano silicon sphere catalyst that load capacity is the loaded with nano zeroth order zinc of 10mg/g
By 1.0g OTAC, 7.0mL 1,3,5-trimethylbenzene is dissolved in 500mL12mmol/L NaOH solution, by mixed solution oil bath magnetic agitation 5h under the condition of 80 DEG C, then 2g ethyl orthosilicate is slowly added in mixed solution, then by the condition lower magnetic force stirring 5h of mixed solution at 80 DEG C, isolated by filtration obtains white precipitate, by washed with methanol, dry under 80 DEG C of conditions; The particulate obtained is transferred in 30mL isopropyl alcohol and 50 μ L APTES mixed solutions, 100 DEG C of continuous heating 5h; Filtering above-mentioned solution, being immersed in 3h in methyl alcohol/concentrated hydrochloric acid mixed solution that volume ratio is 1:80 by filtering the material obtained, dry under centrifugation, vacuum condition, obtain mesoporous nano silicon ball.
According to load capacity, take 208mg zinc chloride, being dissolved in 100mL volume ratio is in the ethanol/water mixed solution of 40/60, add surfactant polyvinylpyrrolidone 0.04g and do dispersant, pH is regulated to be 6 ~ 7 with 1mol/LNaOH, add 10g mesoporous nano silicon ball under mechanical agitation, pass into nitrogen and continue to stir 6h; 100mL 0.25mol/L hydrazine hydrate is dropwise added in mixed solution, and continues to pass into nitrogen in the process of reaction, at room temperature react 3h; Carry out after reaction being separated, clean, dry, obtain the mesoporous nano silicon sphere catalyst that load capacity is the loaded with nano zeroth order zinc of 10mg/g.
Embodiment 3 prepares the mesoporous nano silicon sphere catalyst that load capacity is the loaded with nano zero-valent nickel of 15mg/g
By 1.0g DTAC, 7.0mL 1,3,5-trimethylbenzene is dissolved in 500mL10mmol/L NaOH solution, by mixed solution oil bath magnetic agitation 5h under the condition of 80 DEG C, then 6g ethyl orthosilicate is slowly added in mixed solution, then by the condition lower magnetic force stirring 5h of mixed solution at 80 DEG C, isolated by filtration obtains white precipitate, by washed with methanol, dry under 80 DEG C of conditions; The particulate obtained is transferred in 25mL isopropyl alcohol and 80 μ L APTES mixed solutions, 100 DEG C of continuous heating 5h; Filtering above-mentioned solution, being immersed in 3h in methyl alcohol/concentrated hydrochloric acid mixed solution that volume ratio is 1:50 by filtering the material obtained, dry under centrifugation, vacuum condition, obtain mesoporous nano silicon ball.
According to load capacity, take 467mg nickel nitrate, being dissolved in 100mL volume ratio is in the ethanol/water mixed solution of 40/60, add surfactant to enter polyvinyl alcohol 0.02g and do dispersant, pH is regulated to be 6 ~ 7 with 1mol/L NaOH, add 10g mesoporous nano silicon ball under mechanical agitation, pass into nitrogen and continue to stir 6h; 100mL 0.4mol/L potassium borohydride is dropwise added in mixed solution, and continues to pass into nitrogen in the process of reaction, at room temperature react 3h; Carry out after reaction being separated, clean, dry, obtain the mesoporous nano silicon sphere catalyst that load capacity is the loaded with nano zero-valent nickel of 15mg/g.
Embodiment 4 prepares the SBA-15 catalyst that load capacity is the loaded with nano zeroth order zinc of 10mg/g
According to load capacity, take 247mg zinc sulfate, being dissolved in 100mL volume ratio is in the ethanol/water mixed solution of 40/60, add surfactant Sodium Polyacrylate 0.05g and do dispersant, pH is regulated to be 6 ~ 7 with 1mol/L NaOH, add 10g SBA-15 under mechanical agitation, pass into nitrogen and continue to stir 6h; 100mL 0.5mol/L sodium borohydride is dropwise added in mixed solution, and continues to pass into nitrogen in the process of reaction, at room temperature react 3h; Carry out after reaction being separated, clean, dry, obtain the SBA-15 catalyst that load capacity is the loaded with nano zeroth order zinc of 10mg/g.
Embodiment 5 prepares the MCM-41 catalyst that load capacity is the loaded with nano Zero-valent Iron of 20mg/g
According to load capacity, take 454.5mg frerrous chloride, being dissolved in 100mL volume ratio is in the ethanol/water mixed solution of 40/60, add surfactant polyethylene 0.04g and do dispersant, pH is regulated to be 6 ~ 7 with 1mol/LNaOH, add 10g MCM-41 under mechanical agitation, pass into nitrogen and continue to stir 6h; 100mL 0.25mol/L potassium borohydride is dropwise added in mixed solution, and continues to pass into nitrogen in the process of reaction, at room temperature react 3h; Carry out after reaction being separated, clean, dry, obtain the MCM-41 catalyst that load capacity is the loaded with nano Zero-valent Iron of 20mg/g.
Embodiment 6 prepares the MCM-48 catalyst that load capacity is the loaded with nano zero-valent nickel of 15mg/g
According to load capacity, take 396mg nickelous sulfate, being dissolved in 100mL volume ratio is in the ethanol/water mixed solution of 40/60, add surfactant polyvinylpyrrolidone 0.1g and do dispersant, pH is regulated to be 6 ~ 7 with 1mol/LNaOH, add 10g MCM-48 under mechanical agitation, pass into nitrogen and continue to stir 6h; 100mL 0.3mol/L hydrazine hydrate is dropwise added in mixed solution, and continues to pass into nitrogen in the process of reaction, at room temperature react 3h; Carry out after reaction being separated, clean, dry, obtain the MCM-48 catalyst that load capacity is the loaded with nano zero-valent nickel of 15mg/g.
Embodiment 7 prepares the mesoporous nano silicon sphere catalyst of loaded with nano Zero-valent Iron
The mesoporous nano silicon sphere catalyst of loaded with nano Zero-valent Iron is prepared according to the method for embodiment 1, unlike: surfactant used is respectively Sodium Polyacrylate, polyvinylpyrrolidone, polyvinyl alcohol.
Embodiment 8 different catalysts reducing property is evaluated
Reducing property evaluation is carried out to the material of embodiment 1,7 gained and nano zero valence iron (market purchasing), using 200 μ g/L γ-BHC as target contaminant, catalyst amount is 200mg/L, temperature is room temperature, reaction time is respectively 1h, 2h, 3h, measures the concentration of γ-BHC after reaction.Result shows, the clearance of 4 kinds of materials to γ-BHC reaches 80 ~ 85%, apparently higher than the nano zero valence iron of market purchasing to the removal effect of γ-BHC.In addition, composite is faster to the reduction rate of γ-BHC, and the clearance in 1 ~ 3h is basicly stable; And nano zero valence iron (market purchasing) reduction rate is comparatively slow, along with the prolongation in reaction time, clearance increases to some extent.In table 1.
Table 1 clearance contrast (%)
Embodiment 9 prepares the mesoporous nano silicon sphere catalyst of loaded with nano zeroth order zinc
The mesoporous nano silicon sphere catalyst of loaded with nano zeroth order zinc is prepared according to the method for embodiment 2, unlike: surfactant used is respectively Sodium Polyacrylate, polyethylene glycol, polyvinyl alcohol.
Embodiment 10 different catalysts reducing property is evaluated
Reducing property evaluation is carried out to the material of embodiment 2,9 gained and nano zero-valence zinc (market purchasing), using 200 μ g/L γ-BHC as target contaminant, catalyst amount is 200mg/L, temperature is room temperature, reaction time is respectively 1h, 2h, 3h, measures the concentration of γ-BHC after reaction.Result shows, the clearance of 4 kinds of materials to γ-BHC reaches 84 ~ 87%, apparently higher than the nano zero-valence zinc of market purchasing to the removal effect of γ-BHC.In addition, composite is faster to the reduction rate of γ-BHC, and the clearance in 1 ~ 3h is basicly stable; And nano zero-valence zinc (market purchasing) reduction rate is comparatively slow, along with the prolongation in reaction time, clearance increases to some extent.
Table 2 clearance contrast (%)
Embodiment 11 prepares the mesoporous nano silicon sphere catalyst of loaded with nano zero-valent nickel
The mesoporous nano silicon sphere catalyst of loaded with nano zero-valent nickel is prepared according to the method for embodiment 3, unlike: surfactant used is respectively Sodium Polyacrylate, polyethylene glycol, polyvinylpyrrolidone.
Embodiment 12 different catalysts reducing property is evaluated
Reducing property evaluation is carried out to the material of embodiment 3,11 gained and nano zero-valence nickel (market purchasing), using 200 μ g/L γ-BHC as target contaminant, catalyst amount is 200mg/L, temperature is room temperature, reaction time is respectively 1h, 2h, 3h, measures the concentration of γ-BHC after reaction.Result shows, the clearance of 4 kinds of materials to γ-BHC reaches 85 ~ 90%, apparently higher than the nano zero-valence nickel of market purchasing to the removal effect of γ-BHC.In addition, composite is faster to the reduction rate of γ-BHC, and the clearance in 1 ~ 3h is basicly stable; And nano zero-valence nickel (market purchasing) reduction rate is comparatively slow, along with the prolongation in reaction time, clearance increases to some extent.
Table 3 clearance contrast (%)
Embodiment 13 prepares the SBA-15 catalyst of loaded with nano zeroth order zinc
The SBA-15 catalyst of loaded with nano zeroth order zinc is prepared according to the method for embodiment 4, unlike: surfactant used is respectively polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone.
Embodiment 14 different catalysts reducing property is evaluated
Reducing property evaluation is carried out to the material of embodiment 4,13 gained and nano zero-valence zinc (market purchasing), using 200 μ g/L γ-BHC as target contaminant, catalyst amount is 200mg/L, temperature is room temperature, reaction time is respectively 1h, 2h, 3h, measures the concentration of γ-BHC after reaction.Result shows, the clearance of 4 kinds of materials to γ-BHC reaches 80 ~ 84%, apparently higher than the nano zero-valence zinc of market purchasing to the removal effect of γ-BHC.In addition, composite is faster to the reduction rate of γ-BHC, and the clearance in 1 ~ 3h is basicly stable; And nanometer valency zinc (market purchasing) reduction rate is comparatively slow, along with the prolongation in reaction time, clearance increases to some extent.
Table 4 clearance contrast (%)
Embodiment 15 prepares the MCM-41 catalyst of loaded with nano Zero-valent Iron
The MCM-41 catalyst of loaded with nano Zero-valent Iron is prepared according to the method for embodiment 5, unlike: surfactant used is respectively polyvinyl alcohol, Sodium Polyacrylate, polyvinylpyrrolidone.
Embodiment 16 different catalysts reducing property is evaluated
Reducing property evaluation is carried out to the material of embodiment 5,15 gained and nano zero valence iron (market purchasing), using 200 μ g/L γ-BHC as target contaminant, catalyst amount is 200mg/L, temperature is room temperature, reaction time is respectively 1h, 2h, 3h, measures the concentration of γ-BHC after reaction.Result shows, the clearance of 4 kinds of materials to γ-BHC reaches 83 ~ 87%, apparently higher than the nano zero valence iron of market purchasing to the removal effect of γ-BHC.In addition, composite is faster to the reduction rate of γ-BHC, and the clearance in 1 ~ 3h is basicly stable; And nano zero valence iron (market purchasing) reduction rate is comparatively slow, along with the prolongation in reaction time, clearance increases to some extent.
Table 5 clearance contrast (%)
Embodiment 17 prepares the MCM-48 catalyst of loaded with nano zero-valent nickel
The MCM-48 catalyst of loaded with nano zero-valent nickel is prepared according to the method for embodiment 6, unlike: surfactant used is respectively polyvinyl alcohol, Sodium Polyacrylate, polyethylene glycol.
Embodiment 18 different catalysts reducing property is evaluated
Reducing property evaluation is carried out to the material of embodiment 6,17 gained and nano zero-valence nickel (market purchasing), using 200 μ g/L γ-BHC as target contaminant, catalyst amount is 200mg/L, temperature is room temperature, reaction time is respectively 1h, 2h, 3h, measures the concentration of γ-BHC after reaction.Result shows, the clearance of 4 kinds of materials to γ-BHC reaches 85 ~ 88%, apparently higher than the nano zero-valence nickel of market purchasing to the removal effect of γ-BHC.In addition, composite is faster to the reduction rate of γ-BHC, and the clearance in 1 ~ 3h is basicly stable; And nano zero-valence nickel (market purchasing) reduction rate is comparatively slow, along with the prolongation in reaction time, clearance increases to some extent.
Table 6 clearance contrast (%)
Catalyst prepared by embodiment 19 the present invention and nano zero-valence zinc (iron, nickel) specific area contrast
Surface and lacunarity analysis instrument (Micromeritics ASAP 2020) is adopted to characterize the catalyst of preparation in embodiment 1 ~ 6 and nano zero-valence zinc (iron, nickel).Catalyst and specific area (BET) result of nano zero-valence zinc (iron, nickel) of preparation in embodiment 1 ~ 6 are as shown in table 7.Result shows, in embodiment 1 ~ 6, the catalyst of preparation has close specific area, and specific area is all comparatively large compared with nano zero-valence zinc (iron, nickel), is conducive to the absorption to pollutant.
Table 7BET characterization result
| Material | Specific area (m 2/g) |
| Embodiment 1 | 30.58 |
| Embodiment 2 | 31.26 |
| Embodiment 3 | 28.47 |
| Embodiment 4 | 33.88 |
| Embodiment 5 | 29.15 |
| Embodiment 6 | 30.44 |
| Nano zero-valence zinc | 24.62 |
| Nano zero valence iron | 25.34 |
| Nano zero-valence nickel | 20.55 |
Claims (9)
1. a mesoporous nano Si catalyst for loaded with nano zero-valent metal, is characterized in that, described nano zero-valence metal adopts liquid phase reduction to load on mesoporous nano silicon materials, and described nano zero-valence metal is dispersed in mesoporous nano silicon materials; Described nano zero-valence metal is any one in nano zero valence iron, nano zero-valence zinc or nano zero-valence nickel; Described mesoporous nano silicon materials are any one in SBA-15, MCM-41, MCM-48 or mesoporous nano silicon ball.
2. the mesoporous nano Si catalyst of loaded with nano zero-valent metal according to claim 1, is characterized in that, the load capacity of described nano zero-valence metal in mesoporous nano silicon materials is 10 ~ 20mg/g.
3. the preparation method of mesoporous nano silicon ball according to claim 1, it is characterized in that, preparation process is as follows:
(1) by template molecule, 1,3, it is in 10 ~ 15mmol/L NaOH solution that 5-trimethylbenzene is dissolved in concentration, by mixed solution oil bath magnetic agitation 5h under the condition of 80 DEG C, then ethyl orthosilicate is slowly added in mixed solution, then by the condition lower magnetic force stirring 5h of mixed solution at 80 DEG C, isolated by filtration obtains white precipitate, by washed with methanol, dry under 80 DEG C of conditions, obtain particulate;
(2) particulate that step (1) obtains is transferred in isopropyl alcohol and APTES mixed solution, 100 DEG C of continuous heating 5h;
(3) filtering above-mentioned solution, being immersed in 3h in the methyl alcohol/concentrated hydrochloric acid mixed solution of volume ratio 1:100 ~ 1:50 by filtering the material obtained;
(4) dry under centrifugation, vacuum condition, obtain mesoporous nano silicon ball;
In the preparation method of above-mentioned mesoporous nano silicon ball:
The mass/volume g/ml of described template molecule and 1,3,5-trimethylbenzene is than being 1:7;
Described template molecule is 1:500 with the mass/volume g/ml ratio of NaOH solution;
Described template molecule and the mass ratio of ethyl orthosilicate are 1:2-1:6;
Described template molecule is 1:20 ~ 1:30 with the mass/volume g/ml ratio of isopropyl alcohol;
Described template molecule is 1:50 ~ 1:100 with the mass/volume g/ μ L ratio of APTES;
Described methyl alcohol and the volume ratio of concentrated hydrochloric acid are 1:100 ~ 1:50.
4. the preparation method of mesoporous nano silicon ball according to claim 3, it is characterized in that, described template molecule is any one in softex kw, hexadecyltrimethylammonium chloride, Cetyltrimethylammonium bromide, OTAC, DTAB, DTAC.
5. the preparation method of the mesoporous nano Si catalyst of loaded with nano zero-valent metal according to claim 1, is characterized in that, described nano zero-valence metal adopts liquid phase reduction to load on mesoporous nano silicon materials, and its preparation methods steps is as follows:
(1) take metal soluble-salt according to the load capacity of nano zero-valence metal in mesoporous nano silicon materials, being dissolved in volume ratio is in the ethanol/water mixed solution of 40/60, adds surfactant and does dispersant, regulates pH to be 6 ~ 7 with 1mol/L NaOH;
(2) load capacity according to step (1), adds mesoporous nano silicon materials under mechanical agitation, pass into nitrogen and continue to stir 6h;
(3) 0.25 ~ 0.5mol/L reducing agent is dropwise added in the mixed solution of step (2), continue in course of reaction to pass into nitrogen, at room temperature react 3h;
(4) carry out being separated after reaction, clean, dry, obtain the mesoporous nano Si catalyst of loaded with nano zero-valent metal;
In above-mentioned preparation method:
Metal soluble-salt is 1:100-1:500 with the mass/volume g/ml ratio of ethanol/water 40/60 mixed solution;
The mass ratio of surfactant and mesoporous nano silicon materials is 1:100-1:500;
Reducing agent is 200:1-500:1 with the volume/mass ml/g ratio of metal soluble-salt.
6. the preparation method of the mesoporous nano Si catalyst of loaded with nano zero-valent metal according to claim 5, is characterized in that, the load capacity of described nano zero-valence metal in mesoporous nano silicon materials is 10 ~ 20mg/g.
7. the preparation method of the mesoporous nano Si catalyst of the loaded with nano zero-valent metal according to claim 5 or 6, is characterized in that, described metal soluble-salt is any one in the soluble chloride of iron, zinc or nickel, nitrate or sulfate.
8. the preparation method of the mesoporous nano Si catalyst of the loaded with nano zero-valent metal according to claim 5 or 6, is characterized in that, described surfactant is any one in polyethylene glycol, polyvinylpyrrolidone, Sodium Polyacrylate or polyvinyl alcohol.
9. the preparation method of the mesoporous nano Si catalyst of the loaded with nano zero-valent metal according to claim 5 or 6, is characterized in that, described reducing agent is any one in sodium borohydride, potassium borohydride or hydrazine hydrate.
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| CN108405879A (en) * | 2018-04-02 | 2018-08-17 | 华东理工大学 | A kind of preparation method of nano zero valence iron@meso pore silicon oxide materials |
| CN109142315A (en) * | 2018-08-21 | 2019-01-04 | 江苏大学 | A kind of preparation method and applications of the amino modified MCM-41 material of nanometer of modified by silver |
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| CN105344325A (en) * | 2015-11-04 | 2016-02-24 | 同济大学 | Preparation method of nanometer iron/meso-porous silicon composite material for treating heavy metal-polluted water |
| CN107243358A (en) * | 2017-06-09 | 2017-10-13 | 北京农学院 | A kind of nanoscale zero-valent siderophore and preparation method and application |
| CN107243358B (en) * | 2017-06-09 | 2020-02-21 | 北京农学院 | Nanoscale zero-valent iron carrier and preparation method and application thereof |
| CN108405879A (en) * | 2018-04-02 | 2018-08-17 | 华东理工大学 | A kind of preparation method of nano zero valence iron@meso pore silicon oxide materials |
| CN109142315A (en) * | 2018-08-21 | 2019-01-04 | 江苏大学 | A kind of preparation method and applications of the amino modified MCM-41 material of nanometer of modified by silver |
| CN111167506A (en) * | 2020-03-13 | 2020-05-19 | 重庆文理学院 | Sr2FeO4/SBA-15 composite catalyst material and preparation method thereof |
| CN111359654A (en) * | 2020-03-13 | 2020-07-03 | 重庆文理学院 | Mesoporous supported catalyst material and preparation method thereof |
| CN111359654B (en) * | 2020-03-13 | 2021-02-02 | 重庆文理学院 | Mesoporous supported catalyst material and preparation method thereof |
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