CN116786133B - Preparation method and application of multi-metal atom catalyst - Google Patents
Preparation method and application of multi-metal atom catalyst Download PDFInfo
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- CN116786133B CN116786133B CN202310575871.5A CN202310575871A CN116786133B CN 116786133 B CN116786133 B CN 116786133B CN 202310575871 A CN202310575871 A CN 202310575871A CN 116786133 B CN116786133 B CN 116786133B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 159
- 239000002184 metal Substances 0.000 title claims abstract description 158
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000012876 carrier material Substances 0.000 claims abstract description 123
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000002904 solvent Substances 0.000 claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 238000001179 sorption measurement Methods 0.000 claims abstract description 41
- 239000003999 initiator Substances 0.000 claims abstract description 40
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000010000 carbonizing Methods 0.000 claims abstract description 34
- 239000012266 salt solution Substances 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 19
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 19
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 16
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 80
- 238000003756 stirring Methods 0.000 claims description 64
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 45
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 239000010949 copper Substances 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000000499 gel Substances 0.000 claims description 30
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 235000006408 oxalic acid Nutrition 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 14
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 238000004108 freeze drying Methods 0.000 claims description 13
- 239000000017 hydrogel Substances 0.000 claims description 13
- 229960004995 magnesium peroxide Drugs 0.000 claims description 13
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 13
- 235000005074 zinc chloride Nutrition 0.000 claims description 13
- 239000011592 zinc chloride Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 5
- 239000004113 Sepiolite Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 235000019355 sepiolite Nutrition 0.000 claims description 5
- 229910052624 sepiolite Inorganic materials 0.000 claims description 5
- 229910002566 KAl(SO4)2·12H2O Inorganic materials 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 55
- 239000004964 aerogel Substances 0.000 abstract description 31
- 239000003344 environmental pollutant Substances 0.000 abstract description 23
- 231100000719 pollutant Toxicity 0.000 abstract description 23
- 230000021523 carboxylation Effects 0.000 abstract description 20
- 238000006473 carboxylation reaction Methods 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 229910021645 metal ion Inorganic materials 0.000 abstract description 13
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 238000001784 detoxification Methods 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000000967 suction filtration Methods 0.000 description 24
- 229910017816 Cu—Co Inorganic materials 0.000 description 19
- 230000000694 effects Effects 0.000 description 18
- 229910020632 Co Mn Inorganic materials 0.000 description 16
- 229910020678 Co—Mn Inorganic materials 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 229910052757 nitrogen Chemical group 0.000 description 13
- 238000000227 grinding Methods 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 230000032683 aging Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229910017566 Cu-Mn Inorganic materials 0.000 description 5
- 229910017871 Cu—Mn Inorganic materials 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052717 sulfur Chemical group 0.000 description 2
- 239000011593 sulfur Chemical group 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002355 alkine group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
Abstract
The application relates to a preparation method and application of a multi-metal atom catalyst, wherein the method comprises the steps of mixing a carrier material with a first solvent, adding an initiator, and preparing a carboxylated carrier material by a chemical oxidation method; the multi-metal salt solution is adsorbed on a carboxylation carrier material step by a step adsorption method, and a hydrolytic agent is added to prepare the multi-metal atom loaded aerogel material; dispersing the aerogel material loaded by the multi-metal atoms in a second solvent, adding a template agent, hexamethylenetetramine and water glass, forming a gel product by a solution gel method, and carbonizing to prepare the multi-metal atom catalyst. The multi-metal atom catalyst can be applied to Fenton catalytic oxidation technology and ozone catalytic oxidation technology, can effectively avoid metal ion loss caused by agglomeration of metal atoms in the catalyst and long-time use, improves the selectivity and degradation capability of catalytic reaction on characteristic pollutants, and realizes directional detoxification of the catalytic oxidation technology.
Description
Technical Field
The application relates to the field of wastewater treatment, in particular to a preparation method and application of a multi-metal atom catalyst.
Background
Industrial development produces a large number of refractory toxic organics to be released into the water environment, which seriously threatens the ecological environment and life health. Because of the complex structure of the refractory toxic organic matters, the detoxification and the advanced treatment of the refractory toxic organic matters are difficult to realize by the traditional biochemical treatment process. Advanced oxidation water treatment methods, such as Fenton oxidation and ozone oxidation, are often used for treating various wastewater containing toxic organic matters due to their simple operation and mature technology. However, the advanced oxidation water treatment process has the defects of large dosage of acid and alkali, large amount of sludge, low utilization efficiency of oxidant, poor catalytic selectivity and the like, so that the pollutant detoxification process has high energy consumption and low efficiency, and the national 'double carbon' target is violated.
With the development of nanoscience, the application of novel catalysts based on nanoparticles in the field of wastewater treatment is widely focused. The research shows that the catalyst prepared by loading the metal element on the nano carrier material can effectively improve the catalytic efficiency and the pollutant removal rate in the advanced oxidation water treatment process. However, the supported catalyst has problems of poor metal atom dispersibility, easy metal atom loss, and no selectivity to the target pollutant, especially for a clustered catalyst material having a plurality of active sites.
CN 113289623A discloses "a copper monoatomic catalyst, its preparation method and application". The copper single-atom catalyst prepared by the method can effectively catalyze the selective oxidative coupling of terminal alkyne, and has excellent catalytic effect, but the mesoporous silica has limited number of functional groups in pore channels, so that the grafting rate of copper atom load is lower. CN 110560047B discloses a "highly dispersed monoatomic Pd/mesoporous alumina catalyst, its preparation method and application". The single-atom Pd catalyst with higher dispersion degree can effectively improve the atomic efficiency, furthest utilize noble metal and reduce the cost of the catalyst. But the metal atoms are loaded in a dipping mode, so that the combination stability between the metal atoms and the carrier material is poor, the metal atoms are easy to run off, and the metal atoms have no selectivity for removing target pollutants.
Disclosure of Invention
In order to overcome the defects of the supported catalyst in the prior art, the embodiment of the application provides a preparation method of a multi-metal atom catalyst, and a plurality of metal atoms are uniformly distributed on a carboxylated carrier material by a step-by-step adsorption method, so that the metal atom loading efficiency is improved, and meanwhile, the loss of metal elements is avoided. The catalyst is carbonized and demoulded at high temperature, and the obtained molecular imprinting hole can selectively adsorb and capture target pollutants, so that the directional degradation and detoxification of the pollutants are realized.
In order to solve the technical problems, one technical method adopted in the embodiment of the application is as follows:
in a first aspect, embodiments of the present application provide a method for preparing a multi-metal atom catalyst, including: mixing a carrier material with a first solvent, adding an initiator, and preparing a carboxylated carrier material by a chemical oxidation method; the multi-metal salt solution is adsorbed on a carboxylation carrier material step by a step adsorption method, and a hydrolytic agent is added to prepare the multi-metal atom loaded aerogel material; dispersing the aerogel material loaded by the multi-metal atoms in a second solvent, adding a template agent, hexamethylenetetramine and water glass, forming a gel product by a solution gel method, and carbonizing to prepare the multi-metal atom catalyst.
In some embodiments, after mixing the support material and the first solvent, an initiator is added to produce a carboxylated support material by a chemical oxidation process comprising: mixing the carrier material and the first solvent in a reactor, and stirring for a first preset time; and (3) adding a preset amount of initiator into the reactor for preset times within a first preset time, reacting for 3-5 hours in a water bath at 60-80 ℃, and cooling, filtering, washing and drying to obtain the carboxylated carrier material.
In some embodiments, the multi-metal salt solution comprises a first metal salt solution, a second metal salt solution, and a third metal salt solution, and the step-wise adsorption of the multi-metal salt solution onto the carboxylated support material by a step-wise adsorption method comprises: adding carboxylated carrier material into a first metal salt solution, and reacting for a second preset time to obtain a first product; adding the first product into a second metal salt solution, and reacting for a third preset time to obtain a second product; and adding the second product into a third metal solution, and reacting for a fourth preset time to obtain a third product.
In some embodiments, adding a hydrolysis agent produces a multi-metal atom loaded aerogel material comprising: adding the third product into a hydrolytic agent, and carrying out water bath at 90-98 ℃ for 6h to 8 h to obtain a hydrogel product; freeze-drying the hydrogel product to obtain an aerogel material loaded by multiple metal atoms; wherein the concentration of the hydrolytic agent is 0.1 to 5 percent, and the mass-volume ratio of the third product to the hydrolytic agent is 1:10 to 1:20.
In some embodiments, after forming a gel product by a solution gel process, the carbonized preparation yields a multimetal catalyst comprising: drying the gel product to obtain a dried product; and carbonizing the dried product step by step to obtain the multi-metal atom catalyst.
In some embodiments, carbonizing the dried product by fractional carbonization comprises: carbonizing the dried product at 350-450 ℃ for 2-h-6 h, introducing reducing gas into the dried product, and carbonizing at 750-850 ℃ for 2-h-6 h.
In some embodiments, the support material comprises at least one of activated alumina, diatomaceous earth, and sepiolite; the first solvent is a mixed solution of citric acid, oxalic acid and hypochlorous acid; the initiator is a compound of potassium ferrate, zinc chloride and magnesium peroxide; wherein the mixture ratio of the compound is that the mass ratio of potassium ferrate, zinc chloride and magnesium peroxide is (5-10): (3-5): (5-10).
In some embodiments, the multi-metal salt comprises at least one of a copper metal salt, a cobalt metal salt, and a manganese metal salt; the hydrolysing agent comprises KAl (SO 4 ) 2 ·12H 2 O and FeCl 3 ·6H 2 At least one of O.
In some embodiments, the templating agent includes at least one of pyridine, carbazole, biphenyl, and terphenyl; the second solvent is a mixed solution of absolute ethyl alcohol, ammonia water and diphenyl sulfide.
In a second aspect, embodiments of the present application provide a use of a catalyst prepared as described in the first aspect above in industrial wastewater treatment.
Different from the condition of the related art, the preparation method and the application of the multi-metal atom catalyst provided by the application have the beneficial effects that: the method comprises the steps of mixing a carrier material with a first solvent, adding an initiator, and preparing a carboxylated carrier material by a chemical oxidation method; the multi-metal salt solution is adsorbed on a carboxylation carrier material step by a step adsorption method, and a hydrolytic agent is added to prepare the multi-metal atom loaded aerogel material; dispersing the aerogel material loaded by the multi-metal atoms in a second solvent, adding a template agent, hexamethylenetetramine and water glass, forming a gel product by a solution gel method, and carbonizing to prepare the multi-metal atom catalyst. According to the method, the carrier material is carboxylated, the stability of the carrier material and the adsorptivity of the carrier material to metal atoms can be improved, the multi-metal salt solution is adsorbed on the carboxylated carrier material step by step through a step adsorption method, the agglomeration phenomenon of metal on the carrier surface can be reduced, different metal ions are dispersed and combined on different adsorption sites of the carrier material, the dispersibility of the loaded metal atoms is improved, hexamethylenetetramine has a cage-shaped structure, the loss of the metal atoms can be effectively avoided, in the high-temperature carbonization process of a gel product, silicon element in the gel product is substituted with hexamethylenetetramine and nitrogen and sulfur element in a second solvent and bonded with the metal atoms, so that the stability of the metal atoms is improved, the template agent is carbonized and demoulded, and the obtained molecularly imprinted cavity can selectively adsorb and capture target pollutants, so that the selectivity of the catalyst is improved, and the directional degradation and detoxification of the pollutants are realized.
Drawings
One or more embodiments are illustrated by way of example and not limitation in the figures of the accompanying drawings, in which like references indicate similar elements, and in which the figures of the drawings are not to scale, unless expressly stated otherwise.
Fig. 1 is a flowchart of a preparation method of a multi-metal atom catalyst according to an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
It should be noted that, if not conflicting, the various features in the embodiments of the present application may be combined with each other, which are all within the protection scope of the present application. In addition, while a logical order is illustrated in the flowchart, in some cases, the steps illustrated or described may be performed in an order different than in the flowchart.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
As shown in fig. 1, fig. 1 is a flowchart of a preparation method of a multi-metal atom catalyst according to an embodiment of the present application, where the method includes:
step S1: after the carrier material and the first solvent are mixed, an initiator is added to prepare the carboxylated carrier material through a chemical oxidation method.
The carrier material is a solid material with sex and high dispersivity, has a large surface area, and the micropore surface has the characteristics required by catalysis, such as adsorption performance, surface activity, excellent thermal stability and the like.
In some embodiments, the support material comprises at least one of activated alumina, diatomaceous earth, and sepiolite; the first solvent is a mixed solution of citric acid, oxalic acid and hypochlorous acid, wherein the volume ratio of the citric acid to the oxalic acid to the hypochlorous acid in the mixed solution is 2:1:1; the initiator is a compound of potassium ferrate, zinc chloride and magnesium peroxide, wherein the mixture ratio of the compound is that the mass ratio of the potassium ferrate to the zinc chloride to the magnesium peroxide is (5-10): (3-5): (5-10) and is compounded.
In some embodiments, after mixing the support material and the first solvent, an initiator is added to produce a carboxylated support material by a chemical oxidation process comprising: mixing the carrier material and the first solvent in a reactor, and stirring for a first preset time; and (3) adding a preset amount of initiator into the reactor for preset times within a first preset time, reacting for 3-5 hours in a water bath at 60-80 ℃, and cooling, filtering, washing and drying to obtain the carboxylated carrier material.
The first preset time can be set according to specific conditions, for example, the first preset time can be 30min, a preset amount of initiator is added into the reactor for preset times in the process of stirring the mixed solution in the reactor, for example, the total amount of the initiator is 3g, in the process of stirring, about 0.1g of the initiator is added into the reactor every 1min, after the initiator is added, the mixture is reacted for 4h in a constant-temperature water bath at 60-80 ℃ under the protection of nitrogen, after the reaction is finished, the mixture is cooled to room temperature, and after filtering and washing, the mixture is dried in vacuum at 40-60 ℃ for 8-24 h to obtain the carboxylated carrier material.
In the embodiment of the application, the acidic component and the strong oxidizing component in the first solvent can remove impurities on the surface of the carrier material, open the internal pore canal of the carrier material and activate the functional group of the carrier material. Particularly, oxalic acid in the first solvent enables the carrier material to be oxidized more fully, promotes the surface of the carrier to be oxidized to form carboxyl and other functional groups, and is beneficial to improving the loading capacity and the adsorption capacity of the carrier material on metal atoms. The initiator is added for a plurality of times in a small amount, so that iron, zinc and magnesium elements in the initiator can further activate the carrier material fully and completely, and the activity and stability of the carrier material are improved.
Step S2: the multi-metal salt solution is adsorbed on the carboxylation carrier material step by a step adsorption method, and a hydrolytic agent is added to prepare the multi-metal atom loaded aerogel material.
In some embodiments, the multi-metal salt comprises at least one of a copper metal salt, a cobalt metal salt, and a manganese metal salt; the hydrolysing agent comprises KAl (SO 4 ) 2 ·12H 2 O and FeCl 3 ·6H 2 At least one of O.
In some embodiments, the multi-metal salt solution comprises a first metal salt solution, a second metal salt solution, and a third metal salt solution, and the step-wise adsorption of the multi-metal salt solution onto the carboxylated support material by a step-wise adsorption method comprises: adding carboxylated carrier material into a first metal salt solution, and reacting for a second preset time to obtain a first product; adding the first product into a second metal salt solution, and reacting for a third preset time to obtain a second product; and adding the second product into a third metal solution, and reacting for a fourth preset time to obtain a third product.
It will be appreciated that the multi-metal salt solution may be adsorbed stepwise to the surface of the carboxylated support material and to the interior of the channels by a stepwise adsorption process. For example, the multimetal salt is Cu (NO) 3 ) 2 ·3H 2 O、Co(NO 3 ) 2 ·6H 2 O and Mn (NO) 3 ) 2 The multi-metal salts are respectively prepared into solutions, and carboxylated carrier materials are firstly added into Cu (NO) 3 ) 2 ·3H 2 In O solution, stirring and adsorbing for 10min, filtering the mixed solution to obtain Cu-loaded carboxylated carrier material, and adding the Cu-loaded carboxylated carrier material into Co (NO) 3 ) 2 ·6H 2 In O solution, stirring and adsorbing for 20min, filtering the mixed solution to obtain Cu-Co loaded carboxylated carrier material, and adding the Cu-Co loaded carboxylated carrier material into Mn (NO) 3 ) 2 And (3) in the solution, stirring and adsorbing the mixed solution for 30min, and carrying out suction filtration to obtain the Cu-Co-Mn loaded multi-metal carboxylation carrier material.
In some embodiments, adding a hydrolysis agent produces a multi-metal atom loaded aerogel material comprising: adding the third product into a hydrolytic agent, and carrying out water bath at 90-98 ℃ for 6h to 8 h to obtain a hydrogel product; freeze-drying the hydrogel product to obtain an aerogel material loaded by multiple metal atoms; wherein the concentration of the hydrolytic agent is 0.1 to 5 percent, and the mass-volume ratio of the third product to the hydrolytic agent is 1:10 to 1:20.
In the embodiment of the application, the metal ions are loaded by adopting a step-by-step adsorption method, the metal ions are adsorbed on the carboxylated carrier material step by step through the action of chemical bonds, the agglomeration of the metal ions on the surface of the carboxylated carrier material can be effectively avoided, and different metal ions are dispersed and combined on different adsorption sites of the carboxylated carrier material, so that the metal is uniformly distributed on the surface of the carboxylated carrier material and inside the pore canal in a single form, the catalysis of each metal element can be fully exerted, and the utilization rate of each metal atom is improved. Through adding the hydrolytic agent, the multi-metal atom loaded aerogel material is prepared, and the hydrolytic agent has complexation on metal atoms, so that the prepared catalyst has larger specific surface area and structure.
Step S3: dispersing the aerogel material loaded by the multi-metal atoms in a second solvent, adding a template agent, hexamethylenetetramine and water glass, forming a gel product by a solution gel method, and carbonizing to prepare the multi-metal atom catalyst.
In some embodiments, after forming a gel product by a solution gel process, the carbonized preparation yields a multimetal catalyst comprising: drying the gel product to obtain a dried product; and carbonizing the dried product step by step to obtain the multi-metal atom catalyst. The gel product is required to be dried in vacuum at a temperature of 40-60 ℃ from 8 h to 24 h, and the dried product is carbonized step by step, cooled to room temperature and ground to obtain the multi-metal atom catalyst.
In some embodiments, carbonizing the dried product by fractional carbonization comprises: carbonizing the dried product at 350-450 ℃ for 2-h-6 h, introducing reducing gas into the dried product, and carbonizing at 750-850 ℃ for 2-h-6 h.
Wherein the reducing gas includes any one of carbon monoxide and hydrogen.
In some embodiments, the templating agent includes at least one of pyridine, carbazole, biphenyl, and terphenyl; the second solvent is a mixed solution of absolute ethyl alcohol, ammonia water and diphenyl sulfide.
In the embodiment of the application, the second solvent is mixed solution of absolute ethyl alcohol, ammonia water and diphenyl sulfide, and the azeotropic point of the aqueous solution in the ammonia water can be reduced by adding the absolute ethyl alcohol into the ammonia water, so that the volatilization rate of water molecules is accelerated. The hexamethylenetetramine has a cage-shaped structure, can be used as an adhesive, has a diphenyl sulfide structure and stable chemical properties, and is doped in a catalyst to be beneficial to improving the affinity for benzene ring-containing organic pollutants and improving the removal efficiency of the benzene ring-containing organic pollutants. In the high-temperature step carbonization process, silicon element in the carrier material and nitrogen and sulfur element in hexamethylenetetramine and diphenyl sulfide are subjected to substitution reaction and are bonded with metal atoms, so that the stability of the metal atoms is improved, and the loss of the metal atoms is avoided. The template agent is added in the preparation process of the catalyst, and a molecular imprinting hole with a special size is reserved on the surface of the catalyst after carbonization and demolding, so that characteristic pollutants can be selectively adsorbed, and directional catalytic oxidative degradation is performed, thereby realizing the selective removal of the pollutants. Solves the problem of poor pollutant selectivity removal in the advanced oxidation water treatment method.
The application also provides an application of the catalyst prepared by the preparation method of the multi-metal atom catalyst in industrial sewage treatment.
The following description is made in connection with specific embodiments:
example 1
The preparation process of the multi-metal atom catalyst A specifically comprises the following steps:
(1) 10g of activated alumina is placed in a three-port reaction flask, 100ml of a first solvent is added, and the volume ratio of citric acid with concentration of 20%, oxalic acid with concentration of 20% and hypochlorous acid with concentration of 10% in the first solvent is 2:1:1.
(2) Under the condition of continuous stirring, 3g of initiator (the potassium ferrate: zinc chloride: magnesium peroxide mass ratio is 10:3:5) is compounded, about 0.1g of initiator is added into a reaction vessel every time at intervals of 1min, after the initiator is added, the reaction is carried out in a constant-temperature water bath at 60 ℃ for 4 hours under the protection of nitrogen, after the reaction is finished, the reaction is cooled to room temperature, and after filtration and washing, the carboxylated carrier material is obtained by vacuum drying at 60 ℃ for 8 hours.
(3) 10g of carboxylated support material were added to 1L of Cu (NO) at 100mg/L 3 ) 2 ·3H 2 In O solution, stirring and adsorbing for 10min, and mixingAnd (5) carrying out suction filtration to obtain the Cu-loaded carboxylated carrier material.
(4) Cu-loaded carboxylated carrier material was added to 1L of 200mg/L Co (NO) 3 ) 2 ·6H 2 And in the O solution, stirring and carrying out adsorption reaction for 20min, and then carrying out suction filtration on the mixed solution to obtain the Cu-Co loaded carboxylated carrier material.
(5) The carboxylated carrier material loaded with Cu-Co is added into 1L of Mn (NO) of 300mg/L 3 ) 2 And (3) in the solution, stirring, carrying out adsorption reaction for 30min, and carrying out suction filtration on the mixed solution to obtain the Cu-Co-Mn loaded multi-metal carboxylation carrier material.
(6) The obtained Cu-Co-Mn loaded multi-metal carboxylated carrier material is added into KAl (SO) 4 ) 2 ·12H 2 In O, carrying out water bath reaction for 8 hours at 90 ℃, wherein the mass volume ratio (g: ml) of the multi-metal carboxylation carrier material to the hydrolyzer is 1:20, and obtaining the multi-metal atom loaded aerogel material after freeze drying the formed hydrogel.
(7) Dispersing the aerogel material loaded by the polymetallic atoms in a second solvent (80 ml of absolute ethyl alcohol, 20ml of ammonia water with the concentration of 28% and 2ml of diphenyl sulfide) in an ultrasonic manner, dropwise adding 2g of hexamethylenetetramine and 2ml of water glass solution under the condition of continuous stirring, adding 2g of template agent, mixing and stirring until gel is formed, standing and ageing, drying in vacuum at 60 ℃ for 8 hours, carbonizing the obtained dried product at 400 ℃ for 2 hours under the protection of reducing gas, carbonizing at 800 ℃ for 2 hours, cooling to room temperature, and grinding to obtain the polymetallic atom catalyst A.
Example 2
The preparation process of the multi-metal atom catalyst B specifically comprises the following steps:
(1) 10g of kieselguhr is placed in a three-port reaction bottle, 100ml of a first solvent is added, and the volume ratio of citric acid with the concentration of 20% to oxalic acid with the concentration of 20% to hypochlorous acid with the concentration of 10% in the first solvent is 2:1:1.
(2) 3g of initiator (potassium ferrate: zinc chloride: magnesium peroxide mass ratio 10:3:5) was added to the reaction vessel at 1 minute intervals of about 0.1g each time with continuous stirring. After the initiator is added, the reaction is carried out for 4 hours in a constant-temperature water bath at 60 ℃ under the protection of nitrogen, the reaction is cooled to room temperature after the reaction is finished, and the carboxylated carrier material is obtained after filtration and washing and vacuum drying for 8 hours at 60 ℃.
(3) 10g of carboxylated support material were added to 1L of Cu (NO) at 100mg/L 3 ) 2 ·3H 2 And in the O solution, stirring and carrying out adsorption reaction for 10min, and then carrying out suction filtration on the mixed solution to obtain the Cu-loaded carboxylated carrier material.
(4) The obtained carboxylated carrier material loaded with Cu is added into 1L of Co (NO) with 200mg/L 3 ) 2 ·6H 2 And in the O solution, stirring and carrying out adsorption reaction for 20min, and then carrying out suction filtration on the mixed solution to obtain the Cu-Co loaded carboxylated carrier material.
(5) The carboxylated carrier material loaded with Cu-Co is added into 1L of Mn (NO) of 300mg/L 3 ) 2 And (3) in the solution, stirring, carrying out adsorption reaction for 30min, and carrying out suction filtration on the mixed solution to obtain the Cu-Co-Mn loaded multi-metal carboxylation carrier material.
(6) The obtained Cu-Co-Mn loaded multi-metal carboxylated carrier material is added into KAl (SO) 4 ) 2 ·12H 2 In O, carrying out water bath reaction for 8 hours at 90 ℃, wherein the mass volume ratio (g: ml) of the multi-metal carboxylation carrier material to the hydrolyzer is 1:20, and obtaining the multi-metal atom loaded aerogel material after freeze drying the formed hydrogel.
(7) Dispersing the aerogel material loaded by the polymetallic atoms in a second solvent (80 ml of absolute ethyl alcohol, 20ml of ammonia water with the concentration of 28% and 2ml of diphenyl sulfide) in an ultrasonic manner, dropwise adding 2g of hexamethylenetetramine and 2ml of water glass solution under the condition of continuous stirring, adding 2g of template agent, mixing and stirring until gel is formed, standing and ageing, drying in vacuum at 60 ℃ for 8 hours, carbonizing the obtained dried product at 400 ℃ for 2 hours under the protection of reducing gas, carbonizing at 800 ℃ for 2 hours, cooling to room temperature, and grinding to obtain the polymetallic atom catalyst B.
Example 3
The preparation process of the multi-metal atom catalyst C comprises the following steps:
(1) 10g of sepiolite is placed in a three-port reaction flask, 100ml of a first solvent is added, and the volume ratio of citric acid with concentration of 20%, oxalic acid with concentration of 20% and hypochlorous acid with concentration of 10% in the first solvent is 2:1:1.
(2) 3g of initiator (potassium ferrate: zinc chloride: magnesium peroxide mass ratio 10:3:5) was added to the reaction vessel at 1 minute intervals of about 0.1g each time with continuous stirring. After the initiator is added, the reaction is carried out for 4 hours in a constant-temperature water bath at 60 ℃ under the protection of nitrogen, the reaction is cooled to room temperature after the reaction is finished, and the carboxylated carrier material is obtained after filtration and washing and vacuum drying for 8 hours at 60 ℃.
(3) 10g of carboxylated support material were added to 1L of Cu (NO) at 100mg/L 3 ) 2 ·3H 2 And in the O solution, stirring and carrying out adsorption reaction for 10min, and then carrying out suction filtration on the mixed solution to obtain the Cu-loaded carboxylated carrier material.
(4) Cu-loaded carboxylated carrier material was added to 1L of 200mg/L Co (NO) 3 ) 2 ·6H 2 And in the O solution, stirring and carrying out adsorption reaction for 20min, and then carrying out suction filtration on the mixed solution to obtain the Cu-Co loaded carboxylated carrier material.
(5) The carboxylated carrier material loaded with Cu-Co is added into 1L of Mn (NO) of 300mg/L 3 ) 2 And (3) in the solution, stirring, carrying out adsorption reaction for 30min, and carrying out suction filtration on the mixed solution to obtain the Cu-Co-Mn loaded multi-metal carboxylation carrier material.
(6) The obtained Cu-Co-Mn loaded multi-metal carboxylated carrier material is added into KAl (SO) 4 ) 2 ·12H 2 In O, carrying out water bath reaction for 8 hours at 90 ℃, wherein the mass volume ratio (g: ml) of the multi-metal carboxylation carrier material to the hydrolyzer is 1:20, and obtaining the multi-metal atom loaded aerogel material after freeze drying the formed hydrogel.
(7) Dispersing the aerogel material loaded by the polymetallic atoms in a second solvent (80 ml of absolute ethyl alcohol, 20ml of ammonia water with the concentration of 28% and 2ml of diphenyl sulfide) in an ultrasonic manner, dropwise adding 2g of hexamethylenetetramine and 2ml of water glass solution under the condition of continuous stirring, adding 2g of template agent, mixing and stirring until gel is formed, standing and ageing, drying in vacuum at 60 ℃ for 8 hours, carbonizing the obtained dried product at 400 ℃ for 2 hours under the protection of reducing gas, carbonizing at 800 ℃ for 2 hours, cooling to room temperature, and grinding to obtain the polymetallic atom catalyst C.
Example 4
The preparation process of the multi-metal atom catalyst D specifically comprises the following steps:
(1) 10g of kieselguhr is placed in a three-port reaction bottle, 100ml of a first solvent is added, and the volume ratio of citric acid with the concentration of 20% to oxalic acid with the concentration of 20% to hypochlorous acid with the concentration of 10% in the first solvent is 2:1:1.
(2) 3g of initiator (potassium ferrate: zinc chloride: magnesium peroxide mass ratio 10:3:5) was added to the reaction vessel at 1 minute intervals of about 0.1g each time with continuous stirring. After the initiator is added, the reaction is carried out for 4 hours in a constant-temperature water bath at 60 ℃ under the protection of nitrogen, the reaction is cooled to room temperature after the reaction is finished, and the carboxylated carrier material is obtained after filtration and washing and vacuum drying for 8 hours at 60 ℃.
(3) 10g of carboxylated support material were added to 1L of Cu (NO) at 100mg/L 3 ) 2 ·3H 2 And in the O solution, stirring and carrying out adsorption reaction for 10min, and then carrying out suction filtration on the mixed solution to obtain the Cu-loaded carboxylated carrier material.
(4) The Cu-loaded multimetal carboxylated support material was dosed to a reactor containing KAl (SO) 4 ) 2 ·12H 2 In O, carrying out water bath reaction at 90 ℃ for 8 hours, wherein the mass volume ratio (g: ml) of the multi-metal carboxylated carrier material to the hydrolyzer is 1:20, and obtaining the Cu-loaded aerogel material after freeze drying the formed hydrogel.
(5) Dispersing the aerogel material loaded with Cu in a second solvent (80 ml of absolute ethyl alcohol, 20ml of ammonia water with the concentration of 28% and 2ml of diphenyl sulfide) in an ultrasonic manner, dropwise adding 2g of hexamethylenetetramine and 2ml of water glass solution under the condition of continuous stirring, adding 2g of template agent, mixing and stirring until gel is formed, standing and aging, drying in vacuum at 60 ℃ for 8 hours, carbonizing the obtained dried product at 400 ℃ for 2 hours under the protection of reducing gas, carbonizing at 800 ℃ for 2 hours, cooling to room temperature, and grinding to obtain the multi-metal atom catalyst D.
Example 5
The preparation process of the multi-metal atom catalyst E specifically comprises the following steps:
(1) 10g of activated alumina, kieselguhr and sepiolite are placed in a three-port reaction bottle, 100ml of a first solvent is added, and the volume ratio of citric acid with the concentration of 20% to oxalic acid with the concentration of 20% to hypochlorous acid with the concentration of 10% in the first solvent is 2:1:1.
(2) 3g of initiator (potassium ferrate: zinc chloride: magnesium peroxide mass ratio 10:3:5) was added to the reaction vessel at 1 minute intervals of about 0.1g each time with continuous stirring. After the initiator is added, the reaction is carried out for 4 hours in a constant-temperature water bath at 60 ℃ under the protection of nitrogen, the reaction is cooled to room temperature after the reaction is finished, and the carboxylated carrier material is obtained after filtration and washing and vacuum drying for 8 hours at 60 ℃.
(3) 10g of carboxylated support material were added to 1L of Cu (NO) at 100mg/L 3 ) 2 ·3H 2 And in the O solution, stirring and carrying out adsorption reaction for 10min, and then carrying out suction filtration on the mixed solution to obtain the Cu-loaded carboxylated carrier material.
(4) Cu-loaded carboxylated carrier material was added to 1L of 200mg/L Co (NO) 3 ) 2 ·6H 2 And in the O solution, stirring and carrying out adsorption reaction for 20min, and then carrying out suction filtration on the mixed solution to obtain the Cu-Co loaded carboxylated carrier material.
(5) Adding Cu-Co-loaded multi-metal carboxylated carrier material into KAl (SO) 4 ) 2 ·12H 2 In O, carrying out water bath reaction for 8 hours at 90 ℃, wherein the mass volume ratio (g: ml) of the multi-metal carboxylated carrier material to the hydrolyzer is 1:20, and obtaining the Cu-Co loaded aerogel material after freeze drying the formed hydrogel.
(6) Dispersing aerogel material loaded with Cu-Co in a second solvent (80 ml of absolute ethyl alcohol, 20ml of ammonia water with the concentration of 28% and 2ml of diphenyl sulfide) by ultrasonic, dropwise adding 2g of hexamethylenetetramine and 2ml of water glass solution under the condition of continuous stirring, adding 2g of template agent, mixing and stirring until gel is formed, standing and ageing, vacuum drying at 60 ℃ for 8 hours, carbonizing the obtained dried product at 400 ℃ for 2 hours under the protection of reducing gas, carbonizing at 800 ℃ for 2 hours, cooling to room temperature, and grinding to obtain the multi-metal atom catalyst E.
Example 6
The preparation process of the multi-metal atom catalyst F specifically comprises the following steps:
(1) 10g of kieselguhr is placed in a three-port reaction bottle, 100ml of a first solvent is added, and the volume ratio of citric acid with the concentration of 20% to oxalic acid with the concentration of 20% to hypochlorous acid with the concentration of 10% in the first solvent is 2:1:1.
(2) 3g of initiator (potassium ferrate: zinc chloride: magnesium peroxide mass ratio 10:3:5) was added to the reaction vessel at 1 minute intervals of about 0.1g each time with continuous stirring. After the initiator is added, the reaction is carried out for 4 hours in a constant-temperature water bath at 60 ℃ under the protection of nitrogen, the reaction is cooled to room temperature after the reaction is finished, and the carboxylated carrier material is obtained after filtration and washing and vacuum drying for 8 hours at 60 ℃.
(3) 10g of carboxylated support material were added to 1L of Cu (NO) at 100mg/L 3 ) 2 ·3H 2 And in the O solution, stirring and carrying out adsorption reaction for 10min, and then carrying out suction filtration on the mixed solution to obtain the Cu-loaded carboxylated carrier material.
(4) Cu-loaded carboxylated carrier material was added to 1L of 300mg/L Mn (NO) 3 ) 2 And (3) in the solution, stirring and carrying out adsorption reaction for 30min, and then carrying out suction filtration on the mixed solution to obtain the Cu-Mn loaded multi-metal carboxylation carrier material.
(5) Adding Cu-Mn-loaded multi-metal carboxylated carrier material into KAl (SO) with concentration of 1% 4 ) 2 ·12H 2 In O, carrying out water bath reaction at 90 ℃ for 8 hours, wherein the mass volume ratio (g: ml) of the multi-metal carboxylated carrier material to the hydrolyzer is 1:20, and obtaining the Cu-Mn loaded aerogel material after freeze drying the formed hydrogel.
(6) Dispersing the aerogel material loaded with Cu-Mn in a second solvent (80 ml of absolute ethyl alcohol, 20ml of ammonia water with the concentration of 28% and 2ml of diphenyl sulfide) in an ultrasonic manner, dropwise adding 2g of hexamethylenetetramine and 2ml of water glass solution under the condition of continuous stirring, adding 2g of template agent, mixing and stirring until gel is formed, standing and ageing, drying in vacuum at 60 ℃ for 8 hours, carbonizing the obtained dried product at 400 ℃ for 2 hours under the protection of reducing gas, carbonizing at 800 ℃ for 2 hours, cooling to room temperature, and grinding to obtain the multi-metal atom catalyst F.
Example 7
The preparation process of the multi-metal atom catalyst G specifically comprises the following steps:
(1) 10g of kieselguhr is placed in a three-port reaction bottle, 100ml of a first solvent is added, and the volume ratio of citric acid with the concentration of 20% to oxalic acid with the concentration of 20% to hypochlorous acid with the concentration of 10% in the first solvent is 2:1:1.
(2) 1g of initiator (compounded by potassium ferrate, zinc chloride and magnesium peroxide in a mass ratio of 100:10:1) is added into a reaction vessel at one time under the condition of continuous stirring. After the initiator is added, the reaction is carried out for 4 hours in a constant-temperature water bath at 60 ℃ under the protection of nitrogen, the reaction is cooled to room temperature after the reaction is finished, and the carboxylated carrier material is obtained after filtration and washing and vacuum drying for 8 hours at 60 ℃.
(3) 10g of carboxylated support material were added to 1L of Cu (NO) at 100mg/L 3 ) 2 ·3H 2 And in the O solution, stirring and carrying out adsorption reaction for 10min, and then carrying out suction filtration on the mixed solution to obtain the Cu-loaded carboxylated carrier material.
(4) Cu-loaded carboxylated carrier material was added to 1L of 200mg/L Co (NO) 3 ) 2 ·6H 2 And in the O solution, stirring and carrying out adsorption reaction for 20min, and then carrying out suction filtration on the mixed solution to obtain the Cu-Co loaded carboxylated carrier material.
(5) The carboxylated carrier material loaded with Cu-Co is added into 1L of Mn (NO) of 300mg/L 3 ) 2 And (3) in the solution, stirring, carrying out adsorption reaction for 30min, and carrying out suction filtration on the mixed solution to obtain the Cu-Co-Mn loaded multi-metal carboxylation carrier material.
(6) The Cu-Co-Mn loaded multi-metal carboxylated carrier material was added to a KAl (SO) 4 ) 2 ·12H 2 In O, carrying out water bath reaction at 90 ℃ for 8 hours, wherein the mass volume ratio (g: ml) of the polymetallic carboxylation carrier material to the hydrolyzer is 1:20, and obtaining polymetallic after freeze drying the formed hydrogelBelongs to an atom-loaded aerogel material.
(7) Dispersing the obtained multi-metal atom loaded material in a second solvent (80 ml of absolute ethyl alcohol, 20ml of ammonia water with the concentration of 28% and 2ml of diphenyl sulfide) by ultrasonic, dropwise adding 2G of hexamethylenetetramine and 2ml of water glass solution under the condition of continuous stirring, adding 1G of template agent, mixing and stirring until gel is formed, standing and ageing, drying in vacuum for 8 hours at 60 ℃, carbonizing the obtained dried product for 2 hours at 600 ℃ under the protection of reducing gas, cooling to room temperature, and grinding to obtain the multi-metal atom catalyst G.
Example 8
The preparation process of the multi-metal atom catalyst H specifically comprises the following steps:
(1) 10g of kieselguhr is placed in a three-port reaction bottle, 100ml of a first solvent is added, and the volume ratio of citric acid with the concentration of 20% to oxalic acid with the concentration of 20% to hypochlorous acid with the concentration of 10% in the first solvent is 2:1:1.
(2) 3g of initiator (potassium ferrate: zinc chloride: magnesium peroxide mass ratio 10:1:1) was added to the reaction vessel at 1 minute intervals of about 0.1g each time with continuous stirring. After the initiator is added, the reaction is carried out for 4 hours in a constant-temperature water bath at 60 ℃ under the protection of nitrogen, the reaction is cooled to room temperature after the reaction is finished, and the carboxylated carrier material is obtained after filtration and washing and vacuum drying for 8 hours at 60 ℃.
(3) 10g of carboxylated support material were added to 1L of Cu (NO) at 100mg/L 3 ) 2 ·3H 2 And in the O solution, stirring and carrying out adsorption reaction for 10min, and then carrying out suction filtration on the mixed solution to obtain the Cu-loaded carboxylated carrier material.
(4) Cu-loaded carboxylated carrier material was added to 1L of 200mg/L Co (NO) 3 ) 2 ·6H 2 And in the O solution, stirring and carrying out adsorption reaction for 20min, and then carrying out suction filtration on the mixed solution to obtain the Cu-Co loaded carboxylated carrier material.
(5) The carboxylated carrier material loaded with Cu-Co is added into 1L of Mn (NO) of 300mg/L 3 ) 2 Stirring and adsorbing the mixed solution in the solution for 30min, and then carrying out suction filtration to obtain the Cu-Co-Mn loaded multi-metal carboxylation carrier materialAnd (5) material.
(6) The obtained Cu-Co-Mn adsorbed multi-metal carboxylation carrier material is added into FeCl with concentration of 0.5% 3 ·6H 2 In O, carrying out water bath reaction for 8 hours at 90 ℃, wherein the mass volume ratio (g: ml) of the multi-metal carboxylation carrier material to the hydrolyzer is 1:20, and obtaining the multi-metal atom loaded aerogel material after freeze drying the formed hydrogel.
(7) Dispersing the polymetallic atom-loaded material in a second solvent (80 ml of absolute ethyl alcohol, 20ml of 28% ammonia water and 2ml of diphenyl sulfide) in an ultrasonic manner, dropwise adding 2g of hexamethylenetetramine and 2ml of water glass solution under the condition of continuous stirring, adding 0.5g of template agent, mixing and stirring until gel is formed, standing and ageing, vacuum drying at 60 ℃ for 8 hours, carbonizing the obtained dried product for 2 hours under the protection of reducing gas at 500 ℃, cooling to room temperature, and grinding to obtain the polymetallic atom catalyst H.
Comparative example 1
Other process conditions and experimental procedures of this comparative example 1 were the same as in example 1, except that no initiator was added in step (2), and KAl (SO) was not added in step (6) 4 ) 2 ·12H 2 And (3) adding an O hydrolytic agent, wherein the template agent is not added in the step (7). The preparation process of the multi-metal atom catalyst M specifically comprises the following steps:
(1) 10g of activated alumina is placed in a three-port reaction flask, 100ml of a first solvent is added, and the volume ratio of citric acid with concentration of 20%, oxalic acid with concentration of 20% and hypochlorous acid with concentration of 10% in the first solvent is 2:1:1.
(2) After continuous stirring for 30min, the mixture is reacted for 4 hours in a constant temperature water bath at 60 ℃ under the protection of nitrogen, cooled to room temperature after the reaction is finished, filtered and washed, and dried in vacuum at 60 ℃ for 8 hours to obtain the carboxylated carrier material.
(3) 10g of carboxylated support material were added to 1L of Cu (NO) at 100mg/L 3 ) 2· 3H 2 And in the O solution, stirring and carrying out adsorption reaction for 10min, and then carrying out suction filtration on the mixed solution to obtain the Cu-loaded carboxylated carrier material.
(4) Adding the carboxylated carrier material loaded with Cu to 1L of C with 200mg/Lo(NO 3 ) 2 ·6H 2 And in the O solution, stirring and carrying out adsorption reaction for 20min, and then carrying out suction filtration on the mixed solution to obtain the Cu-Co loaded carboxylated carrier material.
(5) The carboxylated carrier material loaded with Cu-Co is added into 1L of Mn (NO) of 300mg/L 3 ) 2 And (3) in the solution, stirring, carrying out adsorption reaction for 30min, and carrying out suction filtration on the mixed solution to obtain the Cu-Co-Mn loaded multi-metal carboxylation carrier material.
(6) And (3) carrying out water bath reaction on the obtained Cu-Co-Mn loaded multi-metal carboxylation carrier material at 90 ℃ for 8 hours, and freeze-drying to obtain the multi-metal atom loaded aerogel material.
(7) Dispersing the aerogel material loaded by the multi-metal atoms in a second solvent (80 ml of absolute ethyl alcohol, 20ml of ammonia water with the concentration of 28% and 2ml of diphenyl sulfide) in an ultrasonic manner, dropwise adding 2g of hexamethylenetetramine and 2ml of water glass solution under the condition of continuous stirring, mixing and stirring until gel is formed, standing for aging, drying in vacuum at 60 ℃ for 8 hours, carbonizing the obtained dried product at 400 ℃ for 2 hours under the protection of reducing gas, carbonizing at 800 ℃ for 2 hours, cooling to room temperature, and grinding to obtain the multi-metal atom catalyst M.
Comparative example 2
Other process conditions and experimental steps of this comparative example 1 were the same as in example 1, except that steps (3), (4) and (5) of example 1 were combined into one step. The preparation process of the multi-metal atom catalyst N specifically comprises the following steps:
(1) 10g of activated alumina is placed in a three-port reaction flask, 100ml of a first solvent is added, and the volume ratio of citric acid with concentration of 20%, oxalic acid with concentration of 20% and hypochlorous acid with concentration of 10% in the first solvent is 2:1:1.
(2) After continuous stirring for 30min, the mixture is reacted for 4 hours in a constant temperature water bath at 60 ℃ under the protection of nitrogen, cooled to room temperature after the reaction is finished, filtered and washed, and dried in vacuum at 60 ℃ for 8 hours to obtain the carboxylated carrier material.
(3) 1L of Cu (NO) at 100mg/L 3 ) 2 ·3H 2 O solution, 1L Co (NO) 200mg/L 3 ) 2 ·6H 2 O is dissolvedLiquid and 1L of 300mg/L Mn (NO) 3 ) 2 And after the solution is mixed, 10g of carboxylated carrier material is added into the mixed solution, and after stirring and adsorption reaction are carried out for 60min, the mixed solution is filtered by suction, so as to obtain the Cu-Co-Mn loaded multi-metal carboxylated carrier material.
(4) And (3) carrying out water bath reaction on the obtained Cu-Co-Mn loaded multi-metal carboxylation carrier material at 90 ℃ for 8 hours, and freeze-drying to obtain the multi-metal atom loaded aerogel material.
(5) Dispersing the aerogel material loaded by the multi-metal atoms in a second solvent (80 ml of absolute ethyl alcohol, 20ml of ammonia water with the concentration of 28% and 2ml of diphenyl sulfide) in an ultrasonic manner, dropwise adding 2g of hexamethylenetetramine and 2ml of water glass solution under the condition of continuous stirring, mixing and stirring until gel is formed, standing for aging, drying in vacuum at 60 ℃ for 8 hours, carbonizing the obtained dried product at 400 ℃ for 2 hours under the protection of reducing gas, carbonizing at 800 ℃ for 2 hours, cooling to room temperature, and grinding to obtain the multi-metal atom catalyst N.
The multi-metal atom catalysts prepared in examples 1-8, comparative example 1 and comparative example 2 are applied to the test of the effect of Fenton catalytic oxidation process pollutants, and the test method comprises the following steps:
Preparing 10 groups of 1L wastewater to be treated with COD of 300mg/L, wherein the total concentration of target pollutants of nondegradable pyridine, carbazole, biphenyl and terphenyl is 20mg/L, adjusting the pH value of the wastewater to be 7.0, and respectively adding 10g of the multi-metal atom catalysts prepared in examples 1-8, comparative example 1 and comparative example 2 according to COD: h 2 O 2 H is added in a ratio of 1:1 2 O 2 And after stirring and reacting for 30min, detecting the COD removing effect, the target pollutant removing effect and the effluent metal ion concentration of each group of catalysts.
The detection results are as follows:
table 1: the multi-metal atom catalyst prepared by different embodiments has COD removal effect, target pollutant removal effect and effluent metal ion concentration in Fenton catalytic oxidation process.
The multi-metal atom catalysts prepared in examples 1-8, comparative example 1 and comparative example 2 are applied to the ozone catalytic oxidation pollutant effect test, and the test method comprises the following steps:
preparing 10 groups of 1L waste water to be treated with COD of 100mg/L, wherein the total concentration of refractory pyridine, carbazole, biphenyl and terphenyl target pollutants is 10mg/L, adjusting the pH value of the waste water to be 7.0, and respectively adding 10g of the multi-metal atom catalysts prepared in examples 1-8, comparative example 1 and comparative example 2 according to the COD: o (O) 3 O is added in a ratio of 1:1 3 And after stirring and reacting for 30min, detecting the COD removing effect, the target pollutant removing effect and the effluent metal ion concentration of each group of catalysts.
The detection results are as follows:
table 2: the multi-metal atom catalyst prepared by different embodiments has COD removal effect, target pollutant removal effect and effluent metal ion concentration in the ozone catalytic oxidation process.
As can be seen from tables 1 and 2, the metal atom catalysts prepared in examples 1 to 8 are applied to Fenton catalytic oxidation process and ozone catalytic oxidation process, compared with comparative example 1, the removal effect of COD and degradation capability of target pollutants of the catalysts prepared in examples 1 to 8 are obviously improved, and loss of heavy metal ions can be effectively inhibited. The possible reasons are that in the preparation process of the metal atom catalyst, the specific surface area and the metal atom loading capacity of the carrier material are increased by adding the initiator, and the catalytic effect is enhanced by the synergistic effect of multiple metal atoms in the catalyst, so that the COD removal effect is obviously improved, and the selectivity of the catalyst to target pollutants and the degradation capacity of the catalyst to the target pollutants are improved by the reserved molecularly imprinted cavity after the template agent is carbonized and demoulded. Hydrolysis agent KAl (SO) 4 ) 2 ·12H 2 O has complexation effect on metal ions, and the carrier material can form Si-N-S-metal ion coordination bond under high temperature carbonization at 800 ℃, thereby improving the stability of metal atoms on the catalystAvoiding the loss of the catalyst in the using process. Compared with the catalyst obtained by the disposable adsorption method in comparative example 2, the step-by-step adsorption method of examples 1-3 has better COD removal effect, probably because the metal salt solution is adsorbed on the carboxylated carrier material step by step, the agglomeration phenomenon of metal ions on the carrier material is effectively reduced, metal atoms are loaded on the carrier material in single atoms, each metal single atom is fully utilized, and the catalytic activity of the catalyst is improved. Examples 1 to 3 have better COD removal effect than examples 4 to 6, probably because the Cu-Co-Mn supported multi-metal atom catalyst has better synergistic catalytic effect than the Cu-supported multi-metal atom catalyst, the Cu-Co supported multi-metal atom catalyst and the Cu-Mn supported multi-metal atom catalyst. Compared with examples 7-8, examples 1-3 have poor removal effect on COD due to the influence on the performance of the prepared catalyst caused by improper component ratios of the initiator, the hydrolyzer, the template agent and the like in examples 7-8.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and are not limiting thereof; the technical features of the above embodiments or in the different embodiments may also be combined under the idea of the present application, the steps may be implemented in any order, and there are many other variations of the different aspects of the present application as above, which are not provided in details for the sake of brevity; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Claims (8)
1. A method for preparing a multi-metal atom catalyst, comprising:
mixing a carrier material with a first solvent, adding an initiator, and preparing a carboxylated carrier material by a chemical oxidation method;
adding the carboxylated carrier material into copper metal salt solution for reaction by a fractional adsorption method to obtain a first product, and adding the first product into cobalt metal salt solution for reaction to obtain a second product; adding the second product into manganese metal salt solution for reaction to obtain a third product; adding the third product into a hydrolyzer, and carrying out water bath at 90-98 ℃ for 6-8 hours to obtain a hydrogel product;
Freeze-drying the hydrogel product, dispersing in a second solvent, adding a template agent, hexamethylenetetramine and water glass, forming a gel product by a solution gel method, and carbonizing to prepare a multi-metal atom catalyst;
the initiator is a compound of potassium ferrate, zinc chloride and magnesium peroxide;
the hydrolysing agent comprises KAl (SO 4 ) 2 ·12H 2 O and FeCl 3 ·6H 2 At least one of O;
the second solvent is a mixed solution of absolute ethyl alcohol, ammonia water and diphenyl sulfide.
2. The preparation method according to claim 1, wherein the carboxylated carrier material is prepared by a chemical oxidation method by adding an initiator after mixing the carrier material and the first solvent, comprising:
mixing the carrier material and the first solvent in a reactor, and stirring for a first preset time;
and (3) adding a preset amount of initiator into the reactor for preset times within a first preset time, reacting for 3-5 hours in a water bath at 60-80 ℃, and cooling, filtering, washing and drying to obtain the carboxylated carrier material.
3. The preparation method according to claim 1, wherein the concentration of the hydrolysis agent is 0.1% to 5%, and the mass-volume ratio of the third product to the hydrolysis agent is 1g:10ml to 1g:20ml.
4. The preparation method according to claim 1, wherein the multi-metal atom catalyst is prepared by carbonization after forming a gel product by a solution gel method, comprising:
drying the gel product to obtain a dried product;
and carbonizing the dried product step by step to obtain the multi-metal atom catalyst.
5. The process according to claim 4, wherein the step-wise carbonization of the dried product comprises:
carbonizing the dried product at 350-450 ℃ for 2-h-6 h, introducing reducing gas into the dried product, and carbonizing at 750-850 ℃ for 2-h-6 h.
6. The method according to any one of claims 1 to 5, wherein the carrier material comprises at least one of activated alumina, diatomaceous earth, and sepiolite;
the first solvent is a mixed solution of citric acid, oxalic acid and hypochlorous acid;
the compound comprises the following components in percentage by mass: (3-5): (5-10).
7. The method according to any one of claims 1 to 5, wherein the template agent comprises at least one of pyridine, carbazole, biphenyl, and terphenyl.
8. Use of a catalyst prepared by the method for preparing a multimetal catalyst according to any one of claims 1 to 7 in industrial sewage treatment.
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