CN114146700A - 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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- CN114146700A CN114146700A CN202111488281.6A CN202111488281A CN114146700A CN 114146700 A CN114146700 A CN 114146700A CN 202111488281 A CN202111488281 A CN 202111488281A CN 114146700 A CN114146700 A CN 114146700A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 239000004964 aerogel Substances 0.000 title claims abstract description 31
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000010146 3D printing Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002086 nanomaterial Substances 0.000 claims abstract description 28
- 239000000017 hydrogel Substances 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 238000007639 printing Methods 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 230000032683 aging Effects 0.000 claims abstract description 17
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- 238000011049 filling Methods 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000001723 curing Methods 0.000 claims abstract description 6
- 239000000499 gel Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 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
- 238000000016 photochemical curing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 24
- 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
- 239000002243 precursor Substances 0.000 claims description 12
- 238000000352 supercritical drying Methods 0.000 claims description 10
- 238000002210 supercritical carbon dioxide drying Methods 0.000 claims description 9
- 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
- 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
- 238000000034 method Methods 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
- 238000005406 washing Methods 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
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 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
- 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
- 239000000047 product Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- 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
- 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
- 230000000694 effects Effects 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 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
- 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
- 239000013078 crystal Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011259 mixed solution Substances 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
- 230000009286 beneficial effect Effects 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
- 238000010586 diagram Methods 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
- 238000000635 electron micrograph Methods 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation 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
- 238000000926 separation method Methods 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
- 239000011787 zinc oxide Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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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
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- 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
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- C02F2101/345—Phenols
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Abstract
A preparation method of a 3D printing aerogel supported noble metal catalyst comprises the following steps: 1) preparing a premixed solution: mixing an inorganic silicon source, ultraviolet curing resin, whiskers and a metal nano material, and stirring to obtain a premixed solution; 2) firstly, filling a premixed liquid into a resin tank of a three-dimensional photocuring 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 structural 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, the catalyst is integrally formed, and the catalyst can be applied to various scenes and has important significance.
Description
Technical Field
The invention relates to the field of preparation of catalysts, and particularly relates 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, and the like. Such conventional preparation methods have the following disadvantages: 1. noble metals are easy to agglomerate and have poor dispersibility; 2. the reaction conditions are strict; 3. the preparation environment is not green and environment-friendly; 4. long preparation period and the like. According to the invention, the noble metal catalyst can be loaded by 3D printing aerogel, so that the technical defects can be overcome, and the advantages of high noble metal catalyst loading activity, good dispersibility, short period and the like can be 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 purpose, the invention adopts the following technical scheme:
a preparation method of a 3D printing aerogel supported noble metal catalyst comprises the following steps:
1) preparing a premixed solution: mixing an inorganic silicon source, ultraviolet curing resin, whiskers and a metal nano material, and stirring to obtain a premixed solution;
2) firstly, filling a premixed liquid into a resin tank of a three-dimensional photocuring 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; then, aging the printed 3D structural hydrogel, performing solvent replacement on the aged hydrogel, and performing supercritical carbon dioxide drying on the replaced gel; and finally, roasting the product subjected to 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 the inorganic silicon source is not higher than 20%, the content of the curing resin is 70% -80%, the content of the whisker is not higher than 20%, and the content of the metal nano material is not higher than 10% by mass percentage.
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 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.
In the step 1), the metal nano material is prepared as follows: and (3) dripping a reducing agent into the metal salt solution, centrifugally washing and drying.
The metal salt is one or more of a silver precursor, a gold precursor, a palladium precursor, a platinum precursor, a ruthenium precursor, a rhodium precursor and an 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 following beneficial effects:
1. the preparation method comprises the steps of firstly preparing a prefabricated mixed solution, 3D printing the prefabricated mixed solution to obtain hydrogel, then carrying out alcohol exchange, carrying out supercritical drying and roasting to obtain the aerogel supported noble metal catalyst, and providing a new method for preparing the integrated aerogel supported noble metal catalyst by adopting a 3D printing technology, wherein the preparation method is simple, the active components of the catalyst are uniformly dispersed, and the activity of the catalyst is high; the dispersion is uniform, the load capacity adjustable interval is wider, and more active components can be provided to ensure that the active components are uniformly dispersed.
2. According to the invention, a cheap inorganic silicon source is adopted to react with high-pressure carbon dioxide, silicon aerogels with different shapes are prepared through 3D printing, meanwhile, a noble metal catalyst can be loaded, the preparation method is applied to various reaction scenes, and the inorganic aerogel serving as a carrier has a wider application range compared with organic aerogel, can resist high temperature, protects the activity of the catalyst and improves the conversion efficiency of the catalyst.
3. The invention has the advantages that the inorganic silicon source with low cost reacts with the carbon dioxide, the cost of the reactant silicon source can be reduced, the carbon dioxide is used as the raw material, the carbon dioxide is consumed, the purpose of carbon fixation is achieved, and the development concept of carbon neutralization is met.
4. The 3D printing monolithic catalyst prepared by the invention is integrally formed without a die and secondary assembly, has high structure controllability, and effectively improves the whole catalytic activity by designing the structure of the catalyst.
5. The components of the premixed liquid of the 3D printing catalyst can be flexibly prepared according to the type and the content of the metal nano material.
Drawings
FIG. 1 is a schematic illustration of the preparation of the present invention;
FIG. 2 is an electron micrograph (EDS) of the catalyst prepared in example 1;
FIG. 3 is an EDS image of the catalyst prepared in comparative example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects of the present invention clearer and clearer, the present 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 printed aerogel supported noble metal catalyst provided by the invention comprises the following steps:
1) preparing a premixed solution: mixing an inorganic silicon source, ultraviolet curing resin, whiskers and a metal nano material, and stirring to obtain a premixed solution;
2) firstly, filling a premixed liquid into a resin tank of a three-dimensional photocuring 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; then, aging the printed 3D structural hydrogel, performing solvent replacement on the aged hydrogel, and performing supercritical carbon dioxide drying on the replaced gel; and finally, roasting the product subjected to supercritical drying to finally obtain the 3D-printed silica aerogel loaded with the noble metal catalyst.
In the present invention, the whisker is an inorganic whisker, including a ceramic whisker (SiC, potassium titanate, aluminum borate, etc.), an inorganic salt whisker (calcium sulfate, calcium carbonate, etc.), a metal whisker (alumina, zinc oxide, etc.), and the like.
Example 1
(1) 0.1g of potassium tetrachloroplatinate (III) is put into 50mL of pure water to obtain a transparent clear solution, then 8.0mL of 0.15mol/L sodium borohydride solution is dripped into the solution and stirred, then the precipitate is centrifugally separated, washed by pure water and absolute ethyl alcohol for a plurality of times and dried in an oven for a plurality of hours to obtain the metal nano material.
(2) 70 wt% of UV curing resin, 15 wt% of hexanediol, 3 wt% of whisker, 2 wt% of metal nano material and 10 wt% of 0.1mmol of sodium silicate are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the ordered reticular porous cylinder structure into slicing software, filling the printing module with 2MPa of high-pressure carbon dioxide, and printing according to a set model. And (3) aging the printed 3D structural hydrogel at 35 ℃ for 10h, 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, roasting the product after the supercritical drying, removing the rest organic substances at 500 ℃, and finally obtaining the 3D printed integral honeycomb-shaped silicon aerogel supported metal catalyst.
(3) The prepared catalyst is used for intermittent reaction of organic wastewater treated by phenol-like oxidation, and the conditions are as follows: the reaction temperature is 60 ℃, the initial concentration of phenol is 200mg/L, and the removal rate of phenol is 97.2 percent after the reaction is carried out for 90 min.
Comparative example 1
(1) 70 wt% of UV-curable resin, 15 wt% of hexanediol, 3 wt% of whiskers and 12 wt% of 0.1mmol of sodium silicate were mixed and stirred uniformly. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the ordered reticular porous cylinder structure into slicing software, filling the printing module with 2MPa of high-pressure carbon dioxide, and printing according to a set model. And (3) aging the printed 3D structural hydrogel at 35 ℃ for 10h, 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, roasting the product after supercritical drying at 500 ℃, removing the rest organic substances, and finally obtaining the 3D printed integral aerogel.
(2) 0.1g of potassium tetrachloroplatinate (III) is put into 50mL of pure water to obtain a transparent clear solution, then 8.0mL of 0.15mol/L sodium borohydride solution is dripped into the solution and stirred, then the precipitate is centrifugally separated, washed by pure water and absolute ethyl alcohol for a plurality of times and dried in an oven for a plurality of hours to obtain the metal nano material.
(3) And (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 that of the metal nano material added in the step (2) in the embodiment 1.
(4) The prepared catalyst is used for intermittent reaction of organic wastewater treated by phenol-like oxidation, and the conditions are as follows: the reaction temperature is 60 ℃, the initial concentration of phenol is 200mg/L, and the removal rate of phenol is 47.5 percent after the reaction is carried out for 90 min.
As shown in fig. 2 to 3, which are EDS diagrams of the catalysts prepared in example 1 and comparative example 1, respectively, it can be seen that the catalyst component prepared in example 1 is uniformly dispersed, while the catalyst component prepared in comparative example 1 has an agglomeration phenomenon, so that the catalytic activity of example 1 is much higher than that of comparative example 1.
Example 2
(1) 0.05g of potassium tetrachloroaureate (III) is put into 40mL of pure water to obtain a transparent clear solution, then 10.0mL of 0.15mol/L sodium borohydride solution is dripped into the solution and stirred, then the precipitate is centrifugally separated, washed by pure water and absolute ethyl alcohol for a plurality of times and dried in an oven for a plurality of hours to obtain the metal nano material.
(2) 75 wt% of UV curing resin, 14 wt% of hexanediol, 3 wt% of whisker, 1 wt% of metal nano material and 7 wt% of 0.15mmol of sodium silicate are mixed and uniformly stirred, and the loading of the metal nano material is controlled to be 0.1%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the ordered reticular porous cylinder structure into slicing software, filling the printing module with high-pressure carbon dioxide of 2.5Mpa, and printing according to a set model. And (3) aging the printed 3D structural hydrogel at 40 ℃ for 16h, 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, roasting the product after the supercritical drying, removing the rest organic substances at 700 ℃, and finally obtaining the 3D printed integral honeycomb-shaped silicon aerogel supported metal catalyst.
(3) The prepared catalyst is used for intermittent reaction of organic wastewater treated by phenol-like oxidation, and the conditions are as follows: the reaction temperature is 70 ℃, the initial concentration of phenol is 200mg/L, and the removal rate of phenol is 99.1 percent after reaction for 70 min.
Example 3
(1) And (2) putting 0.08g of silver nitrate into 50mL of pure water to obtain a transparent clear solution, then dripping 10.0mL0.15mol/L hydrazine hydrate solution into the solution, stirring the solution, then performing centrifugal separation on a precipitate, washing the precipitate by using pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 73 wt% of UV curing resin, 12 wt% of acetone, 3 wt% of whisker, 1.5 wt% of metal nano material and 10.5 wt% of 0.2mmol of sodium silicate are mixed and uniformly stirred, and the loading of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the ordered reticular porous cylinder structure into slicing software, filling the printing module with 2MPa of high-pressure carbon dioxide, and printing according to a set model. And (3) aging the printed 3D structural hydrogel at the aging temperature of 40 ℃ for 12h, 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, roasting the product after the supercritical drying, and removing the rest organic substances at the roasting temperature of 600 ℃ to finally obtain the 3D printed integral honeycomb-shaped silicon aerogel supported metal catalyst.
(3) The prepared catalyst is used for intermittent reaction of organic wastewater treated by phenol-like oxidation, and the conditions are as follows: the reaction temperature is 50 ℃, the initial concentration of phenol is 200mg/L, and the removal rate of phenol is 96.3 percent after the reaction is carried out for 60 min.
Example 4
And (2) putting 0.05g of ruthenium trichloride into 40mL of pure water to obtain a transparent clear solution, then dripping 6.0mL of 0.3mol/L sodium citrate solution, stirring, then precipitating, centrifugally separating, washing with pure water and absolute ethyl alcohol for several times, and drying in an oven for several hours to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 13 wt% of methanol, 2 wt% of crystal whisker, 2 wt% of metal nano material and 3 wt% of 0.2mmol of sodium silicate are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.1%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the ordered reticular porous cylinder structure into slicing software, filling the printing module with high-pressure carbon dioxide of 3.0Mpa, and printing according to a set model. And (3) 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 the hydrogel is 30L each time, performing supercritical carbon dioxide drying on the replaced alcogel, roasting the product after the supercritical drying, and removing the rest organic substances at the roasting temperature of 600 ℃ to finally obtain the 3D printed integral honeycomb-shaped silicon aerogel supported metal catalyst.
(3) The prepared catalyst is used for intermittent reaction of organic wastewater treated by phenol-like oxidation, and the conditions are as follows: the reaction temperature is 70 ℃, the initial concentration of phenol is 300mg/L, and the removal rate of phenol is 97.8 percent after the reaction is carried out for 100 min.
Example 5
0.03g of potassium tetrachloropalladate (III) is put into 50mL of pure water to obtain a transparent clear solution, then 7.0mL of 0.25mol/L ascorbic acid solution is dropped and stirred, then the precipitate is centrifugally separated, washed with pure water and absolute ethyl alcohol for a plurality of times and dried in an oven for a plurality of hours to obtain the metal nano material.
(2) 71 wt% of UV curing resin, 20 wt% of methanol, 2 wt% of crystal whisker, 2 wt% of metal nano material and 5 wt% of 0.3mmol of sodium silicate are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.15%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the ordered reticular porous cylinder structure into slicing software, filling the printing module with high-pressure carbon dioxide of 2.0Mpa, and printing according to a set model. And (3) aging the printed 3D structural hydrogel at the aging temperature of 40 ℃ for 12h, 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, roasting the product after the supercritical drying, removing the rest organic substances at the roasting temperature of 700 ℃, and finally obtaining the 3D printed integral honeycomb-shaped silicon aerogel supported metal catalyst.
(3) The prepared catalyst is used for intermittent reaction of organic wastewater treated by phenol-like oxidation, and the conditions are as follows: the reaction temperature is 70 ℃, the initial concentration of phenol is 250mg/L, and the removal rate of phenol is 96.3 percent after the reaction is carried out for 90 min.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A preparation method of a 3D printing aerogel supported noble metal catalyst is characterized by comprising the following steps:
1) preparing a premixed solution: mixing an inorganic silicon source, ultraviolet curing resin, whiskers and a metal nano material, and stirring to obtain a premixed solution;
2) firstly, filling a premixed liquid into a resin tank of a three-dimensional photocuring 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; then, aging the printed 3D structural hydrogel, performing solvent replacement on the aged hydrogel, and performing supercritical carbon dioxide drying on the replaced gel; and finally, roasting the product subjected to supercritical drying to finally obtain the 3D-printed silica aerogel loaded with the noble metal catalyst.
2. The preparation method of the 3D printing aerogel supported noble metal catalyst as claimed in claim 1, wherein: 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.
3. The preparation method of the 3D printing aerogel supported noble metal catalyst as claimed in claim 1, wherein: in the step 1), the content of the inorganic silicon source is not higher than 20%, the content of the curing resin is 70% -80%, the content of the whisker is not higher than 20%, and the content of the metal nano material is not higher than 10% by mass percentage.
4. The preparation method of the 3D printing aerogel supported noble metal catalyst as claimed in claim 1, wherein: in the step 2), the pressure of the carbon dioxide is 0.8-4 MPa.
5. The preparation method of the 3D printing aerogel supported noble metal catalyst as claimed in claim 1, wherein: in the step 2), the aging time is 1-24 h, and the aging temperature is 10-80 ℃; the roasting temperature is 400-1000 ℃.
6. The preparation method of the 3D printing aerogel supported noble metal catalyst as claimed in claim 1, wherein: in the step 2), the solvent comprises at least one of methanol, ethanol, acetone and hexanediol.
7. The preparation method of the 3D printing aerogel supported noble metal catalyst as claimed in claim 1, wherein: in the step 2), the temperature of 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.
8. The preparation method of the 3D printing aerogel supported noble metal catalyst as claimed in claim 1, wherein: in the step 1), the metal nano material is prepared as follows: and (3) dripping a reducing agent into the metal salt solution, centrifugally washing and drying.
9. The method for preparing the 3D printing aerogel supported noble metal catalyst according to claim 8, wherein the method comprises the following steps: the metal salt is one or more of a silver precursor, a gold precursor, a palladium precursor, a platinum precursor, a ruthenium precursor, a rhodium precursor and an 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.
10. The method for preparing the 3D printing aerogel supported noble metal catalyst according to claim 8, wherein the method comprises 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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| Publication number | Priority date | Publication date | Assignee | Title |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559196A (en) * | 2014-12-29 | 2015-04-29 | 大连理工常熟研究院有限公司 | Colorless and transparent light-cured 3D printing material |
| CN111484021A (en) * | 2020-05-08 | 2020-08-04 | 厦门大学 | Preparation method of silicon dioxide aerogel |
| CN111825879A (en) * | 2019-04-10 | 2020-10-27 | 中国科学院化学研究所 | Precursor solution for 3D printing of aerogel and 3D printing method |
| CN112707402A (en) * | 2020-12-31 | 2021-04-27 | 中国人民解放军国防科技大学 | Silica aerogel ink for 3D direct-writing printing and preparation method thereof |
| CN113289626A (en) * | 2021-04-25 | 2021-08-24 | 南京师范大学 | Preparation method and application of 3D printing monolithic catalyst applied to Fenton-like/persulfate system |
-
2021
- 2021-12-08 CN CN202111488281.6A patent/CN114146700B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559196A (en) * | 2014-12-29 | 2015-04-29 | 大连理工常熟研究院有限公司 | Colorless and transparent light-cured 3D printing material |
| CN111825879A (en) * | 2019-04-10 | 2020-10-27 | 中国科学院化学研究所 | Precursor solution for 3D printing of aerogel and 3D printing method |
| CN111484021A (en) * | 2020-05-08 | 2020-08-04 | 厦门大学 | Preparation method of silicon dioxide aerogel |
| CN112707402A (en) * | 2020-12-31 | 2021-04-27 | 中国人民解放军国防科技大学 | Silica aerogel ink for 3D direct-writing printing and preparation method thereof |
| CN113289626A (en) * | 2021-04-25 | 2021-08-24 | 南京师范大学 | Preparation method and application of 3D printing monolithic catalyst applied to Fenton-like/persulfate system |
Non-Patent Citations (1)
| Title |
|---|
| TING LIU ET AL.: "Pd Nanoparticle-Decorated 3D-Printed Hierarchically Porous TiO2 Scaffolds for the Efficient Reduction of a Highly Concentrated 4‑Nitrophenol Solution", 《ACS APPLIED MATERIALS & INTERFACES》, vol. 12, pages 2 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4344774A1 (en) * | 2022-09-27 | 2024-04-03 | Vito NV | Three-dimensional porous structure and method for producing it |
| WO2024068790A1 (en) * | 2022-09-27 | 2024-04-04 | Vito Nv | Three-dimensional porous structure and method for producing it |
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Denomination of invention: A preparation method of 3D printing aerogel supported noble metal catalyst Granted publication date: 20231229 Pledgee: China Everbright Bank Limited by Share Ltd. Xiamen branch Pledgor: Xiamen Dianshi New Materials Co.,Ltd. Registration number: Y2024980013613 |