CN114146700B - Preparation method of 3D printing aerogel supported noble metal catalyst - Google Patents
Preparation method of 3D printing aerogel supported noble metal catalyst Download PDFInfo
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- CN114146700B CN114146700B CN202111488281.6A CN202111488281A CN114146700B CN 114146700 B CN114146700 B CN 114146700B CN 202111488281 A CN202111488281 A CN 202111488281A CN 114146700 B CN114146700 B CN 114146700B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000004964 aerogel Substances 0.000 title claims abstract description 28
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 24
- 238000010146 3D printing Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 239000002086 nanomaterial Substances 0.000 claims abstract description 28
- 239000000017 hydrogel Substances 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 20
- 238000007639 printing Methods 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 230000032683 aging Effects 0.000 claims abstract description 15
- 238000011049 filling Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000011068 loading method Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001723 curing Methods 0.000 claims abstract description 8
- 239000000499 gel Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000004965 Silica aerogel Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000000352 supercritical drying Methods 0.000 claims description 10
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000012696 Pd precursors Substances 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002210 supercritical carbon dioxide drying Methods 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 238000003848 UV Light-Curing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
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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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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Abstract
The preparation method of the 3D printing aerogel supported noble metal catalyst comprises the following steps: 1) Preparing a premix: mixing an inorganic silicon source, ultraviolet light curing resin, whiskers and a metal nano material, and stirring to obtain a premix; 2) Firstly, filling the premix into a resin tank of a three-dimensional light curing molding 3D printer, and loading an STL file with a required 3D structure into slicing software; filling the printing module with carbon dioxide, and printing according to the set model; aging the printed 3D structure hydrogel, performing solvent replacement on the aged hydrogel, and drying the replaced gel by supercritical carbon dioxide; and finally, roasting the dried product to obtain the 3D printed silica aerogel loaded with the noble metal catalyst. The preparation method is simple, the active components of the catalyst are uniformly dispersed, the catalytic activity is higher, a die is not needed, and the catalyst can be integrally formed and can be applied to various scenes and has important significance.
Description
Technical Field
The invention relates to the field of catalyst preparation, in particular to a preparation method of a 3D printing aerogel supported noble metal catalyst.
Background
At present, the preparation method of the aerogel supported noble metal catalyst mainly adopts: impregnation, precipitation, ion exchange, etc. Such conventional preparation methods have the following disadvantages: 1. noble metals are easy to agglomerate and have poor dispersibility; 2. the reaction condition is strict; 3. the preparation environment is not green and environment-friendly; 4. long preparation period and the like. According to the invention, the technical defects can be overcome by 3D printing of the aerogel supported noble metal catalyst, and the advantages of high noble metal catalyst supporting activity, good dispersibility, short period and the like are realized.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a preparation method of a 3D printing aerogel supported noble metal catalyst.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the 3D printing aerogel supported noble metal catalyst comprises the following steps:
1) Preparing a premix: mixing an inorganic silicon source, ultraviolet light curing resin, whiskers and a metal nano material, and stirring to obtain a premix;
2) Firstly, filling the premix into a resin tank of a three-dimensional light curing molding 3D printer, and loading an STL file with a required 3D structure into slicing software; filling the printing module with carbon dioxide, and printing according to the set model; aging the printed 3D structure hydrogel, replacing the aged hydrogel with a solvent, and drying the replaced gel with supercritical carbon dioxide; and finally roasting the product after supercritical drying to finally obtain the 3D printed silica aerogel loaded with the noble metal catalyst.
In the step 1), the concentration of the inorganic silicon source is 0.1-0.8M, and the inorganic silicon source is one or two of sodium silicate and potassium silicate.
In the step 1), the content of inorganic silicon source is not higher than 20%, the content of solidified resin is 70% -80%, the content of whisker is not higher than 20%, and the content of metal nano material is not higher than 10% by mass percent.
In the step 2), the pressure of the carbon dioxide is 0.8-4 MPa.
In the step 2), the aging time is 1-24 h, and the aging temperature is 10-80 ℃; the roasting temperature is 400-1000 ℃.
In the step 2), the solvent comprises at least one of methanol, ethanol, acetone and hexanediol.
In the step 2), the temperature of the solvent replacement is 10-60 ℃, the mass ratio of the solvent to the gel is 1:1-20:1, and the replacement times are 1-5.
In step 1), the preparation of the metal nanomaterial is as follows: and (3) dropwise adding a reducing agent into the metal salt solution, centrifugally washing, and drying.
The metal salt is one or more of silver precursor, gold precursor, palladium precursor, platinum precursor, ruthenium precursor, rhodium precursor and iridium precursor; the reducing agent is one or more than two of hydrazine hydrate, sodium borohydride, sodium citrate, sodium tartrate, ascorbic acid and sodium phosphite.
The concentration of the metal salt solution is 0.01-0.5 mol/L; the concentration of the reducing agent is 0.01-0.5 mol/L.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. the preparation method comprises the steps of preparing a prefabricated mixed solution, 3D printing the prefabricated mixed solution to obtain hydrogel, performing alcohol exchange, performing supercritical drying and roasting to obtain the aerogel supported noble metal catalyst, and providing a novel method for preparing the integrated aerogel supported noble metal catalyst by adopting a 3D printing technology, wherein the preparation is simple, the active components of the catalyst are uniformly dispersed, and the catalyst activity is high; the dispersion is uniform, the adjustable interval of the load capacity is wider, and more active components are provided, so that the active components are uniformly dispersed.
2. According to the invention, the cheap inorganic silicon source is adopted to react with the high-pressure carbon dioxide, the silicon aerogel with different shapes is prepared through 3D printing, and meanwhile, the noble metal catalyst can be loaded, so that the silicon aerogel is applied to various reaction scenes, and the inorganic aerogel has a wider application range compared with the organic aerogel as a carrier, can resist high temperature, protect the activity of the catalyst, and improve the conversion efficiency of the catalyst.
3. The invention reacts with the carbon dioxide by using the low-cost inorganic silicon source, thereby not only reducing the cost of the reactant silicon source, but also consuming the carbon dioxide by using the carbon dioxide as the raw material, achieving the purpose of carbon fixation and conforming to the development concept of carbon neutralization.
4. The 3D printing integral catalyst prepared by the invention does not need a die, is integrally formed, does not need secondary assembly, has high structural adjustability, and effectively improves the integral catalytic activity by designing the catalyst structure.
5. The premix liquid components of the 3D printing catalyst can be flexibly prepared according to the types and the contents of the metal nano materials.
Drawings
FIG. 1 is a schematic illustration of the preparation of the present invention;
FIG. 2 is an EDS diagram of the catalyst prepared in example 1;
FIG. 3 is an EDS diagram of the catalyst prepared in comparative example 1.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the accompanying drawings and embodiments.
As shown in fig. 1, the preparation method of the 3D printing aerogel supported noble metal catalyst provided by the invention comprises the following steps:
1) Preparing a premix: mixing an inorganic silicon source, ultraviolet light curing resin, whiskers and a metal nano material, and stirring to obtain a premix;
2) Firstly, filling the premix into a resin tank of a three-dimensional light curing molding 3D printer, and loading an STL file with a required 3D structure into slicing software; filling the printing module with carbon dioxide, and printing according to the set model; aging the printed 3D structure hydrogel, replacing the aged hydrogel with a solvent, and drying the replaced gel with supercritical carbon dioxide; and finally roasting the product after supercritical drying to finally obtain the 3D printed silica aerogel loaded with the noble metal catalyst.
In the present invention, the whiskers are inorganic whiskers including ceramic whiskers (SiC, potassium titanate, aluminum borate, etc.), inorganic salt whiskers (calcium sulfate, calcium carbonate, etc.), metal whiskers (alumina, zinc oxide, etc.), etc.
Example 1
(1) And adding 0.1g of potassium tetrachloroplatinate (III) into 50mL of pure water to obtain a transparent clear solution, then dripping 8.0mL of 0.15mol/L sodium borohydride solution into the clear solution, stirring the solution, precipitating and centrifugally separating the solution, washing the solution with the pure water and absolute ethyl alcohol for a plurality of times, and drying the solution in an oven for a plurality of hours to obtain the metal nano material.
(2) 70wt% of UV curing resin, 15wt% of hexanediol, 3wt% of whisker, 2wt% of metal nano material and 10wt% of sodium silicate with the weight percentage of 0.1mmol are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with an ordered mesh porous cylinder structure into slicing software, filling a printing module with high-pressure carbon dioxide of 2MPa, and printing according to a set model. Aging the printed 3D structural hydrogel at 35 ℃ for 10 hours, replacing the aged hydrogel with absolute ethyl alcohol for three times continuously, wherein the usage amount of the hydrogel is 30L each time, performing supercritical carbon dioxide drying on the replaced alcogel, performing product roasting on the product after supercritical drying, and removing other organic substances at 500 ℃ to finally obtain the 3D printed integral honeycomb silicon aerogel supported metal catalyst.
(3) The catalyst prepared by the method is used for the intermittent reaction of the phenol-like oxidation treatment organic wastewater, and the conditions are as follows: under normal pressure and air atmosphere, the reaction temperature is 60 ℃, the initial concentration of phenol is 200mg/L, and the removal rate of phenol is 97.2% after 90 minutes of reaction.
Comparative example 1
(1) 70wt% of UV-curable resin, 15wt% of hexanediol, 3wt% of whisker and 0.1mmol of sodium silicate, 12wt% were mixed and stirred uniformly. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with an ordered mesh porous cylinder structure into slicing software, filling a printing module with high-pressure carbon dioxide of 2MPa, and printing according to a set model. Aging the printed 3D structural hydrogel at 35 ℃ for 10 hours, replacing the aged hydrogel with absolute ethyl alcohol for three times continuously, wherein the usage amount of the hydrogel is 30L each time, performing supercritical carbon dioxide drying on the replaced alcogel, performing product roasting on the product after supercritical drying, and removing other organic substances at 500 ℃ to finally obtain the 3D printing monolithic aerogel.
(2) And adding 0.1g of potassium tetrachloroplatinate (III) into 50mL of pure water to obtain a transparent clear solution, then dripping 8.0mL of 0.15mol/L sodium borohydride solution into the clear solution, stirring the solution, precipitating and centrifugally separating the solution, washing the solution with the pure water and absolute ethyl alcohol for a plurality of times, and drying the solution in an oven for a plurality of hours to obtain the metal nano material.
(3) Mixing and mechanically stirring the metal nano material obtained in the step (2) and the aerogel obtained in the step (1), and controlling the mass of the metal nano material to be equal to the mass of the metal nano material added in the step (2) in the embodiment 1.
(4) The catalyst prepared by the method is used for the intermittent reaction of the phenol-like oxidation treatment organic wastewater, and the conditions are as follows: under normal pressure and air atmosphere, the reaction temperature is 60 ℃, the initial concentration of phenol is 200mg/L, and the removal rate of phenol is 47.5% after 90min of reaction.
As shown in fig. 2 to 3, which are respectively the EDS diagrams of the catalysts prepared in example 1 and comparative example 1, it can be seen from the figures that the catalyst components prepared in example 1 are uniformly dispersed, and the catalyst components of comparative example 1 have an agglomeration phenomenon, so that the catalytic activity of example 1 is much higher than that of comparative example 1.
Example 2
(1) Adding 0.05g of potassium tetrachloro (III) to 40mL of pure water to obtain a transparent clear solution, then dripping 10.0mL of 0.15mol/L sodium borohydride solution into the clear solution, stirring the solution, precipitating and centrifugally separating the solution, washing the solution with pure water and absolute ethyl alcohol for a plurality of times, and drying the solution in an oven for a plurality of hours to obtain the metal nano material.
(2) 75wt% of UV curing resin, 14wt% of hexanediol, 3wt% of whisker, 1wt% of metal nano material and 7wt% of sodium silicate with the weight percentage of 0.15mmol are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.1%. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with an ordered mesh porous cylinder structure into slicing software, filling a printing module with high-pressure carbon dioxide of 2.5Mpa, and printing according to a set model. Aging the printed 3D structural hydrogel at 40 ℃ for 16 hours, replacing the aged hydrogel with absolute ethyl alcohol for three times continuously, wherein the usage amount of the hydrogel is 30L each time, performing supercritical carbon dioxide drying on the replaced alcogel, performing product roasting on the product after supercritical drying, and removing other organic substances at 700 ℃ to finally obtain the 3D printed integral honeycomb silicon aerogel supported metal catalyst.
(3) The catalyst prepared by the method is used for the intermittent reaction of the phenol-like oxidation treatment organic wastewater, and the conditions are as follows: under normal pressure and air atmosphere, the reaction temperature is 70 ℃, the initial concentration of phenol is 200mg/L, and the phenol removal rate is 99.1% after 70min of reaction.
Example 3
(1) And adding 0.08g of silver nitrate into 50mL of pure water to obtain a transparent clear solution, then dripping 10.0mL of 0.15mol/L hydrazine hydrate solution into the clear solution, stirring the solution, precipitating, centrifuging the solution, washing the solution with pure water and absolute ethyl alcohol for several times, and drying the solution in an oven for several hours to obtain the metal nano material.
(2) 73wt% of UV curing resin, 12wt% of acetone, 3wt% of whisker, 1.5wt% of metal nano material and 10.5wt% of 0.2mmol of sodium silicate are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with an ordered mesh porous cylinder structure into slicing software, filling a printing module with high-pressure carbon dioxide of 2MPa, and printing according to a set model. Aging the printed 3D structural hydrogel at 40 ℃ for 12 hours, replacing the aged hydrogel with absolute ethyl alcohol for three times continuously, wherein the usage amount of the hydrogel is 35L each time, performing supercritical carbon dioxide drying on the replaced alcogel, performing product roasting on the product after supercritical drying, and removing other organic substances at 600 ℃ to finally obtain the 3D printed integral honeycomb silicon aerogel supported metal catalyst.
(3) The catalyst prepared by the method is used for the intermittent reaction of the phenol-like oxidation treatment organic wastewater, and the conditions are as follows: under normal pressure and air atmosphere, the reaction temperature is 50 ℃, the initial concentration of phenol is 200mg/L, and the phenol removal rate is 96.3% after 60min of reaction.
Example 4
0.05g of ruthenium trichloride is put into 40mL of pure water to obtain a transparent clear solution, then 6.0mL of 0.3mol/L sodium citrate solution is dripped into the clear solution and stirred, then precipitation and centrifugal separation are carried out, pure water and absolute ethyl alcohol are used for washing for a plurality of times, and the metal nano material is obtained after drying in an oven for a plurality of hours.
(2) 80wt% of UV curing resin, 13wt% of methanol, 2wt% of whisker, 2wt% of metal nano material and 3wt% of sodium silicate with the weight percentage of 0.2mmol are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.1%. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with an ordered mesh porous cylinder structure into slicing software, filling a printing module with high-pressure carbon dioxide of 3.0Mpa, and printing according to a set model. Aging the printed 3D structural hydrogel at the aging temperature of 30 ℃ for 8 hours, replacing the aged hydrogel with absolute ethyl alcohol for three times continuously, wherein the usage amount of each time is 30L, performing supercritical carbon dioxide drying on the replaced alcogel, performing product roasting on the product after supercritical drying, and removing other organic substances at the roasting temperature of 600 ℃ to finally obtain the 3D printed integral honeycomb silicon aerogel supported metal catalyst.
(3) The catalyst prepared by the method is used for the intermittent reaction of the phenol-like oxidation treatment organic wastewater, and the conditions are as follows: under normal pressure and air atmosphere, the reaction temperature is 70 ℃, the initial concentration of phenol is 300mg/L, and the removal rate of phenol is 97.8% after 100min of reaction.
Example 5
And adding 0.03g of potassium tetrachloropalladate (III) into 50mL of pure water to obtain a transparent clear solution, then dripping 7.0mL of 0.25mol/L ascorbic acid solution into the clear solution, stirring the solution, performing precipitation and centrifugal separation, washing the solution with pure water and absolute ethyl alcohol for a plurality of times, and drying the solution in an oven for a plurality of hours to obtain the metal nano material.
(2) 71wt% of UV curing resin, 20wt% of methanol, 2wt% of whisker, 2wt% of metal nano material and 5wt% of sodium silicate with the weight percentage of 0.3mmol are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.15%. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with an ordered mesh porous cylinder structure into slicing software, filling a printing module with high-pressure carbon dioxide of 2.0Mpa, and printing according to a set model. Aging the printed 3D structural hydrogel at 40 ℃ for 12 hours, replacing the aged hydrogel with absolute ethyl alcohol for three times continuously, wherein the usage amount of the hydrogel is 35L each time, performing supercritical carbon dioxide drying on the replaced alcogel, performing product roasting on the product after supercritical drying, and removing other organic substances at 700 ℃ to finally obtain the 3D printed integral honeycomb silicon aerogel supported metal catalyst.
(3) The catalyst prepared by the method is used for the intermittent reaction of the phenol-like oxidation treatment organic wastewater, and the conditions are as follows: under normal pressure and air atmosphere, the reaction temperature is 70 ℃, the initial concentration of phenol is 250mg/L, and the phenol removal rate is 96.3% after 90min of reaction.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, i.e., the invention is not to be limited to the details of the invention.
Claims (6)
1. The preparation method of the 3D printing aerogel supported noble metal catalyst is characterized by comprising the following steps of:
1) Preparing a premix: mixing an inorganic silicon source, ultraviolet light curing resin, whiskers and a metal nano material, and stirring to obtain a premix;
2) Firstly, filling the premix into a resin tank of a three-dimensional light curing molding 3D printer, and loading an STL file with a required 3D structure into slicing software; filling the printing module with carbon dioxide, and printing according to the set model; aging the printed 3D structure hydrogel, replacing the aged hydrogel with a solvent, and drying the replaced gel with supercritical carbon dioxide; finally roasting the product after supercritical drying to finally obtain 3D printed silica aerogel loaded with the noble metal catalyst;
in the step 1), the concentration of the inorganic silicon source is 0.1-0.8M, and the inorganic silicon source is one or two of sodium silicate and potassium silicate;
in the step 1), the content of inorganic silicon source is not higher than 20 percent, the content of solidified resin is 70-80 percent, the content of whisker is not higher than 20 percent, and the content of metal nano material is not higher than 10 percent according to mass percent;
in the step 2), the pressure of the carbon dioxide is 0.8-4 MPa;
in step 1), the preparation of the metal nanomaterial is as follows: dripping a reducing agent into the metal salt solution, centrifugally washing and drying;
the metal salt is one or more than two of silver precursor, gold precursor, palladium precursor, platinum precursor, ruthenium precursor, rhodium precursor and iridium precursor.
2. The method for preparing the 3D printing aerogel supported noble metal catalyst according to claim 1, which is characterized by comprising the following steps: in the step 2), the aging time is 1-24 h, and the aging temperature is 10-80 ℃; the roasting temperature is 400-1000 ℃.
3. The method for preparing the 3D printing aerogel supported noble metal catalyst according to claim 1, which is characterized by comprising the following steps: in the step 2), the solvent comprises at least one of methanol, ethanol, acetone and hexanediol.
4. The method for preparing the 3D printing aerogel supported noble metal catalyst according to claim 1, which is characterized by comprising the following steps: in the step 2), the temperature of the solvent replacement is 10-60 ℃, the mass ratio of the solvent to the gel is 1:1-20:1, and the replacement times are 1-5 times.
5. The method for preparing the 3D printing aerogel supported noble metal catalyst according to claim 1, which is characterized by comprising the following steps: the reducing agent is one or more than two of hydrazine hydrate, sodium borohydride, sodium citrate, sodium tartrate, ascorbic acid and sodium phosphite.
6. The method for preparing the 3D printing aerogel supported noble metal catalyst according to claim 1, which is characterized by comprising the following steps: the concentration of the metal salt solution is 0.01-0.5 mol/L; the concentration of the reducing agent is 0.01-0.5 mol/L.
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