CN116078376A - Supported noble metal formaldehyde removal catalyst with high-density synergistic catalytic active site, and preparation method and application thereof - Google Patents
Supported noble metal formaldehyde removal catalyst with high-density synergistic catalytic active site, and preparation method and application thereof Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 98
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 60
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- -1 organic acid salt Chemical class 0.000 claims abstract description 10
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- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000005470 impregnation Methods 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 60
- 239000007789 gas Substances 0.000 claims description 22
- 239000010931 gold Substances 0.000 claims description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 230000007547 defect Effects 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 8
- ALHHYLLHZKAXCW-UHFFFAOYSA-H dipotassium;platinum(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[K+].[K+].[Pt+4] ALHHYLLHZKAXCW-UHFFFAOYSA-H 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 5
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- 238000003756 stirring Methods 0.000 claims description 5
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910003771 Gold(I) chloride Inorganic materials 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002082 metal nanoparticle Substances 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- XJMWHXZUIGHOBA-UHFFFAOYSA-N azane;propanoic acid Chemical compound N.CCC(O)=O XJMWHXZUIGHOBA-UHFFFAOYSA-N 0.000 claims description 2
- LDMNYTKHBHFXNG-UHFFFAOYSA-H disodium;platinum(4+);hexahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Pt+4] LDMNYTKHBHFXNG-UHFFFAOYSA-H 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims description 2
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 claims description 2
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- BYFKUSIUMUEWCM-UHFFFAOYSA-N platinum;hexahydrate Chemical compound O.O.O.O.O.O.[Pt] BYFKUSIUMUEWCM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 18
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01J23/48—Silver or gold
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Abstract
The invention belongs to the technical field of catalytic materials, and discloses a supported noble metal formaldehyde removal catalyst with high-density synergistic catalytic active sites, and a preparation method and application thereof. The invention is characterized in that noble metal salt and/or noble metal acid and organic acid salt are dissolved in hydroxide aqueous solution to obtain noble metal solution, a metal oxide carrier is added into the noble metal solution and stirred for impregnation, and an impregnated sample is obtained after solvent evaporation and drying; and carrying out reduction heat treatment on the impregnated sample to obtain the catalyst. According to the invention, the precious metal precursor is preferably matched with the complexing agent, so that the precious metal dispersion degree is effectively improved, and meanwhile, the 'hydrogen overflow effect' of the precious metal phase is utilized to create rich oxygen vacancies at the adjacent positions, so that the high-density precious metal/oxygen vacancy synergetic catalytic active site is constructed. The supported noble metal formaldehyde removal catalyst provided by the invention has better comprehensive performance than the formaldehyde oxidation catalyst reported at present due to the construction of high-density synergistic catalytic active sites.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a supported noble metal formaldehyde removal catalyst with high-density synergistic catalytic active sites, and a preparation method and application thereof.
Background
Formaldehyde is one of the most common and toxic indoor air pollutants, and exposure to formaldehyde exceeding conditions can cause a variety of serious diseases, such as: asthma, nasopharyngeal carcinoma, leukemia, etc., constitute a great threat to human health. Therefore, developing a safe and efficient formaldehyde removal technology is critical to improving the air quality of the residence environment and reducing health risks. In the existing formaldehyde removal technology, the catalytic oxidation method becomes the preferred scheme because of the advantages of high removal efficiency, non-toxic products, energy conservation and the like. The core of the development of catalytic oxidation for formaldehyde removal is to develop an efficient and low-cost formaldehyde oxidation catalyst to realize the completion of oxidative degradation of formaldehyde into CO under the condition of room temperature 2 And H 2 O。
Formaldehyde oxidation catalysts have been developed over twenty years to form supported noble metals (Pt, au, pd, ag, etc.), non-noble metal oxides (MnO) 2 ，CeO 2 And Co 3 O 4 Etc.) two major branches. Although the non-noble metal oxide is low in price, the activity of the non-noble metal oxide is generally low, and formaldehyde can be catalyzed to be completely oxidized under the temperature condition of 60 ℃ or higher; in contrast, noble metal catalysts mostly have excellent low-temperature catalytic activity, and partially supported noble metal catalysts can catalyze complete oxidation of formaldehyde at room temperature, but commercial applications thereof are subject to high material costs. In view of the large activity difference between the two, the supported noble metal catalyst is still the formaldehyde oxidation catalyst with the current most application prospect. In recent years, the development of efficient and inexpensive supported noble metal catalysts has become a mainstream trend for developing formaldehyde catalytic oxidation technology. According to the report of the literature, the formaldehyde oxidation catalytic activity of the supported noble metal catalyst can be effectively improved by optimizing the dispersion state of noble metal particles and regulating and controlling the components and the structure of the carrier. However, in general, the catalytic activity of noble metal catalysts is far from satisfactory for practical purposes (in terms of unit mass of noble metal catalytic reactionLower rate) [ appl. Surf. Sci.475 (2019) 237-255)]. Therefore, the development of an advanced design concept and a controllable synthesis method of a supported noble metal catalyst still advance the key problems to be solved in the practical process of formaldehyde catalytic oxidation technology.
Disclosure of Invention
In view of the above drawbacks and deficiencies of the prior art, a primary object of the present invention is to provide a supported noble metal formaldehyde removal catalyst having high density of synergistic catalytic active sites. The catalyst provided by the invention has the characteristics of high-dispersively distributed noble metal nano particles and oxygen vacancy enrichment in the interface region of the noble metal particles and the carrier oxide, provides high-density noble metal/oxygen vacancy synergetic catalytic active sites, can efficiently and stably catalyze formaldehyde oxidative decomposition at room temperature, and shows excellent comprehensive catalytic performance.
The invention also aims to provide a preparation method of the supported noble metal formaldehyde removal catalyst with high-density synergistic catalytic active sites. The method has the advantages of easily available raw materials, simple operation, and convenient mass production.
The aim of the invention is achieved by the following technical scheme:
a preparation method of a supported noble metal formaldehyde removal catalyst with high-density synergistic catalytic active sites comprises the following steps:
dissolving noble metal salt and/or noble metal acid and organic acid salt in a hydroxide aqueous solution to obtain a noble metal solution, adding a metal oxide carrier into the noble metal solution, stirring and impregnating, and evaporating and drying the noble metal salt and/or the noble metal acid and the organic acid salt by a solvent to obtain an impregnated sample; the impregnated sample is subjected to reduction heat treatment (noble metal components are reduced into a metal phase, meanwhile, an oxide phase with a rich defect structure is prepared, and in-situ compounding of two phases is realized) to obtain the supported noble metal formaldehyde removal catalyst with high-density synergistic catalytic active sites.
Preferably, the noble metal salt is sodium hexahydroxy platinum (IV) acid Na 2 [Pt(OH) 6 ]Potassium hexahydroxyplatinate (IV) K 2 [Pt(OH) 6 ]Sodium chloroplatinate Na 2 PtCl 6 Platinum nitrate Pt (NO) 3 ) 2 Platinum hydroxide Pt (OH) 4 Gold hydroxide Au (OH) 3 At least one of (a) and (b); the noble metal acid is hexahydroxyplatinic acid (IV) H 2 [Pt(OH) 6 ]Chloroplatinic acid H 2 PtCl 6 Chloroauric acid H 2 AuCl 4 At least one of (a) and (b); the organic acid salt refers to ammonium formate CH 5 NO 2 Ammonium acetate C 2 H 7 NO 2 Ammonium propionate C 3 H 9 NO 2 At least one of (a) and (b); the hydroxide refers to an alkali metal hydroxide.
Further preferably, the alkali metal hydroxide comprises at least one of LiOH, naOH, KOH, rbOH, csOH.
Preferably, the total concentration of noble metal salts and/or noble metal acids in the noble metal solution is 0.2-100mM; the concentration of the organic acid salt in the noble metal solution is 0.2-200mM; OH in the noble metal solution - The concentration is 1 multiplied by 10 -4 -5×10 3 mM; the metal oxide carrier is TiO 2 、TiO 2 ·xH 2 O、Ti 2 O 3 、CeO 2 、MnO 2 、Fe 2 O 3 、Co 3 O 4 At least one of (a) and (b); the ratio of the mass of noble metal in the noble metal salt and/or noble metal acid to the mass of the metal oxide carrier is 0.1-5wt%.
Preferably, the time of the dipping and stirring is 0.1-5h.
Preferably, the atmosphere of the reduction heat treatment is 1-100% of hydrogen/argon mixed gas, the temperature of the reduction heat treatment is 100-400 ℃, and the time of the reduction heat treatment is 0.5-5h.
The supported noble metal formaldehyde-removing catalyst with the high-density synergistic catalytic active sites prepared by the preparation method comprises a noble metal active phase and a metal oxide carrier phase with oxygen-enriched defects, wherein the noble metal active phase is distributed on the surface of the metal oxide carrier phase with the oxygen-enriched defects in a dispersed nanoparticle form.
Preferably, the synergistic catalytic active sites refer to noble metal nanoparticles and goldBelongs to a neighboring region consisting of oxygen defects in the oxide carrier; the noble metal is at least one of Pt and Au; the metal oxide carrier with oxygen-enriched defect is TiO 2 、TiO 2 ·xH 2 O、Ti 2 O 3 、CeO 2 、MnO 2 、Fe 2 O 3 、Co 3 O 4 At least one of them.
Preferably, the nanoparticle size of the noble metal active phase is 0.2 to 3nm.
The application of the supported noble metal formaldehyde removal catalyst with high-density synergistic catalytic active sites in formaldehyde catalytic oxidation.
The design principle of the invention is as follows:
early, the applicant used Pt/TiO 2-x The active site of the supported noble metal formaldehyde oxidation catalyst is explored for the model catalyst, and the result shows that the formaldehyde oxidation is carried out on Pt/TiO 2-x The activation of O at the Pt site occurs at the interface by a synergistic catalytic mechanism 2 Generating active O, adjacent oxygen vacancies of which provide formaldehyde adsorption sites; meanwhile, researches show that the hydrogen atmosphere reduction heat treatment can utilize the hydrogen overflow effect of Pt sites to form adjacent oxygen vacancies, and can effectively create Pt/TiO 2-x Interface, is an ideal method for preparing supported Pt catalyst [ ACS catalyst.12 (2022) 5565-5573)]. Based on the mechanism recognition and the hydrogen overflow effect, the invention provides the supported noble metal formaldehyde removal catalyst with high-density synergistic catalytic active sites, and provides a simple and easy preparation method for realizing the catalyst. Firstly, a metal complex capable of effectively improving the dispersity of noble metal is preferably selected as a noble metal precursor sample loaded with oxide by an impregnation method; and then, separating out a noble metal phase by regulating and controlling the conditions of the hydrogen atmosphere reduction heat treatment, and forming adjacent oxygen vacancies by utilizing the hydrogen overflow effect of noble metal sites, thereby constructing noble metal/oxygen vacancy synergetic catalytic active sites. In summary, the supported noble metal catalyst provided by the invention can provide high-density noble metal/oxygen vacancy synergetic catalytic active sites for formaldehyde oxidation.
Compared with the prior art, the invention has the following advantages:
(1) The method and the material provided by the invention have the advantages of effectively optimizing the intrinsic activity and the number of active sites. The dispersity of noble metal is effectively improved by optimizing the metal complex, and the oxygen vacancies are created at the adjacent positions of the metal phase by utilizing the hydrogen overflow effect of the metal phase while the metal phase is reduced and separated out in the hydrogen-containing atmosphere, so that the high-density noble metal/oxygen vacancy synergetic catalytic active site is formed.
(2) The preparation method has the advantages of easily available raw materials, simple process and convenient mass production.
(3) The supported noble metal catalyst provided by the invention has excellent room-temperature formaldehyde oxidation catalytic activity, good stability and moisture resistance, and comprehensive catalytic performance superior to that of the supported noble metal catalyst reported at present.
Drawings
FIG. 1 shows the Pt loading of 0.5wt% on TiO obtained in example 1 of the present invention 2 Catalyst (noted as Pt/TiO) 2 ) High angle annular dark field-scanning transmission electron micrographs.
FIG. 2 shows the Pt/TiO composition obtained in example 1 of the present invention 2 X-ray photoelectron spectrum of the catalyst in O1s region.
FIG. 3 shows the Pt/TiO composition obtained in example 1 of the present invention 2 Formaldehyde catalytic oxidation performance diagram of the catalyst.
FIG. 4 shows the Pt/TiO composition obtained in example 1 of the present invention 2 Results of stability test of catalyst.
FIG. 5 shows the Pt/TiO composition obtained in example 1 of the present invention 2 The moisture resistance test result graph of the catalyst.
FIG. 6 shows the loading of 0.5wt% Pt on CeO obtained in example 2 of the present invention 2 Catalyst (noted as Pt/CeO) 2 ) High angle annular dark field-scanning transmission electron micrographs.
FIG. 7 shows Pt/CeO obtained in example 2 of the present invention 2 X-ray photoelectron spectrum of the catalyst in O1s region.
FIG. 8 shows Pt/CeO obtained in example 2 of the present invention 2 Formaldehyde catalytic oxidation performance diagram of the catalyst.
FIG. 9 is a schematic illustration of an embodiment of the present inventionPt/CeO obtained in example 2 2 Results of stability test of catalyst.
FIG. 10 shows Pt/CeO obtained in example 2 of the present invention 2 The moisture resistance test result graph of the catalyst.
FIG. 11 shows the loading of 0.5wt% Au on TiO obtained in example 3 of the present invention 2 Catalyst (noted as Au/TiO) 2 ) High angle annular dark field-scanning transmission electron micrographs.
FIG. 12 shows Au/TiO of example 3 of the present invention 2 X-ray photoelectron spectrum of the catalyst in O1s region.
FIG. 13 shows Au/TiO of example 3 of the present invention 2 Formaldehyde catalytic oxidation performance diagram of the catalyst.
FIG. 14 shows Au/TiO of example 3 of the present invention 2 Results of stability test of catalyst.
FIG. 15 shows Au/TiO of example 3 of the present invention 2 The moisture resistance test result graph of the catalyst.
FIG. 16 shows the Pt loading of 0.5wt% on TiO of comparative example 1 according to the present invention 2 Catalyst (noted as Pt/TiO) 2 -1) high angle annular dark field-scanning transmission electron micrographs.
FIG. 17 shows the Pt/TiO ratio obtained in comparative example 1 of the present invention 2 -1 formaldehyde catalytic oxidation performance profile of the catalyst.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments and the scope of the present invention are not limited thereto.
TiO in the following examples 2 Is from Jiangsu Xianfeng nano materials science and technology Co., ltd;
CeO in the following examples 2 Is from Shanghai Michlin Biochemical technology Co.
Example 1
(1) And (3) preparing a catalyst:
Pt/TiO 2 and (3) synthesizing a catalyst: will be 0.0256mmol Na 2 [Pt(OH) 6 ]And 0.08mmol C 2 H 7 NO 2 Dissolved in 50mL of 0.1M NaOH solution, followed by addition of1.0g TiO 2 Stirring for 1h, collecting a solid sample by a solvent evaporation mode, and carrying out vacuum drying at 80 ℃ for 6h to obtain an impregnated sample; impregnated sample at H 2 Heating to 200deg.C under Ar (1/10) atmosphere at a heating rate of 5deg.C for min -1 Cooling to room temperature after 1h of constant temperature treatment to obtain the target catalyst.
(2) Structural/elemental oxygen chemical state characterization of the catalyst:
Pt/TiO obtained in this example 2 High angle annular dark field-scanning transmission electron micrograph of the catalyst (FIG. 1), tiO 2 A large number of fine dispersed Pt nano particles are uniformly distributed on the surface, and the size is 0.8-2 nm.
X-ray photoelectron spectroscopy (FIG. 2), the signal belonging to defective oxygen appears in the O1s orbit spectrogram, and the Pt/TiO is proved 2 The catalyst surface has a plurality of oxygen vacancies.
(3) The catalyst Pt/TiO obtained in this example 2 Catalytic performance test:
Pt/TiO at different temperatures 2 The change in catalytic activity of the catalyst (FIG. 3) shows that under high space velocity conditions (800L g) cat - 1 h -1 ) 120ppm formaldehyde can be completely degraded into CO at the reaction temperature of 20 DEG C 2 And H 2 O, indicating that it has excellent low temperature catalytic activity; in addition, the mass ratio of the catalyst is up to 113.0 mu mol g under the reaction condition of room temperature (25 ℃), and the catalyst is used for preparing the catalyst Pt - 1 s -1 This catalytic activity is at the top level in the reported formaldehyde oxidation catalysts. Activity test conditions: the gas component is a mixture of 120ppm formaldehyde and synthetic air, and the gas space velocity is 800L g cat -1 h -1 。
FIG. 4 shows Pt/TiO 2 The stability test result shows that the activity of the catalyst is not obviously attenuated after 24h isothermal measurement, thus indicating that the catalyst has good stability. Stability test conditions: the gas component is a mixture of 120ppm formaldehyde and synthetic air, and the gas space velocity is 1200L g cat -1 h -1 The temperature was 25 ℃.
FIG. 5 shows Pt/TiO 2 The results of the moisture resistance test of the catalyst show small fluctuation of the activity of the catalyst under different humidity conditions, which indicates that the catalyst has good moisture resistance. Moisture resistance test conditions: the gas component is a mixture of 120ppm formaldehyde and synthetic air, and the gas space velocity is 1200L g cat -1 h -1 The temperature was 25 ℃.
Example 2
(1) And (3) preparing a catalyst:
in the synthesis method of this example, only TiO was used 2 Change to CeO 2 The remaining preparation conditions were identical to those of example 1.
(2) Structural/elemental oxygen chemical state characterization of the catalyst:
Pt/CeO obtained in this example 2 High angle annular dark field-scanning transmission electron micrograph of catalyst (FIG. 6), ceO 2 A large number of fine dispersed Pt nano particles are uniformly distributed on the surface, and the size is 0.9-2 nm.
X-ray photoelectron spectroscopy (FIG. 7), the signal belonging to the defective oxygen appears in the O1s orbit spectrogram, and the Pt/CeO is proved 2 The catalyst surface has a plurality of oxygen vacancies.
(3) The catalyst Pt/CeO obtained in this example 2 Catalytic performance test:
Pt/CeO at different temperatures 2 The change in catalytic activity of the catalyst (FIG. 8) shows that at high space velocity (800L g) cat - 1 h -1 ) 120ppm of formaldehyde can be completely degraded into CO at the reaction temperature of 25 DEG C 2 And H 2 O, the catalyst has excellent low-temperature catalytic activity; in addition, the mass ratio of the catalyst is as high as 95.2 mu mol g under the reaction condition of room temperature (25 ℃), and the catalyst is used for preparing the catalyst Pt -1 s -1 This catalytic activity is superior to the formaldehyde oxidation catalysts reported so far. Activity test conditions: the gas component is a mixture of 120ppm formaldehyde and synthetic air, and the gas space velocity is 800L g cat -1 h -1 。
FIG. 9 shows Pt/CeO 2 The stability test result of the catalyst shows that the activity of the catalyst is not obviously attenuated after 24 hours of isothermal measurement,the catalyst has good stability. Stability test conditions: the gas component is a mixture of 120ppm formaldehyde and synthetic air, and the gas space velocity is 1200L g cat -1 h -1 The temperature was 25 ℃.
FIG. 10 shows Pt/CeO 2 The results of the moisture resistance test of the catalyst show small fluctuation of the activity of the catalyst under different humidity conditions, which indicates that the catalyst has good moisture resistance. Moisture resistance test conditions: the gas component is a mixture of 120ppm formaldehyde and synthetic air, and the gas space velocity is 1200L g cat -1 h -1 The temperature was 25 ℃.
Example 3
(1) And (3) preparing a catalyst:
in the synthesis method of this example, only Na was used 2 [Pt(OH) 6 ]Change to H 2 AuCl 4 The remaining preparation conditions were identical to those of example 1.
(2) Structural/elemental oxygen chemical state characterization of the catalyst:
Au/TiO obtained in this example 2 High angle annular dark field-scanning transmission electron micrograph of the catalyst (FIG. 11), tiO 2 A large number of tiny dispersed Au nano particles are uniformly distributed on the surface, and the size is 0.9-2 nm.
X-ray photoelectron spectroscopy (FIG. 12), the signal belonging to the defective oxygen appears in the O1s orbit spectrogram, proving Au/TiO 2 The catalyst surface has a plurality of oxygen vacancies.
(3) The catalyst Au/TiO obtained in this example 2 Catalytic performance test:
Au/TiO at different temperatures 2 The change in catalytic activity of the catalyst (FIG. 13) shows that under high space velocity conditions (800L g) cat -1 h -1 ) 120ppm of formaldehyde can be completely degraded into CO at the reaction temperature of 25 DEG C 2 And H 2 O, the catalyst has excellent low-temperature catalytic activity; in addition, the mass ratio of the catalyst is up to 88.6 mu mol g under the reaction condition of room temperature (25 ℃), and the catalyst is used for preparing the catalyst Pt -1 s -1 This catalytic activity is superior to the supported Au catalysts that have been reported so far. Activity test conditions:the gas component is a mixture of 120ppm formaldehyde and synthetic air, and the gas space velocity is 800L g cat -1 h -1 。
FIG. 14 shows Au/TiO 2 The stability test result shows that the activity of the catalyst is not obviously attenuated after 24h isothermal measurement, thus indicating that the catalyst has good stability. Stability test conditions: the gas component is a mixture of 120ppm formaldehyde and synthetic air, and the gas space velocity is 1000L g cat -1 h -1 The temperature was 25 ℃.
FIG. 15 shows Au/TiO 2 The results of the moisture resistance test of the catalyst show small fluctuation of the catalyst activity under different humidity conditions, which indicates that the catalyst has good moisture resistance. Moisture resistance test conditions: the gas component is a mixture of 120ppm formaldehyde and synthetic air, and the gas space velocity is 1000L g cat -1 h -1 The temperature was 25 ℃.
Comparative example 1
(1) And (3) preparing a catalyst:
in the synthesis method of this example, only the organic acid salt was not added, and the other preparation conditions were the same as those of example 1.
(2) Structural characterization of the catalyst:
Pt/TiO obtained in this example 2 -1 high angle annular dark field-scanning transmission electron micrograph of catalyst (FIG. 16), tiO 2 The Pt particle size on the surface was mostly concentrated at 5nm, which is far larger than that in example 1 (0.8-2 nm). The density of Pt/oxygen vacancy co-catalytic sites that can be constructed in this case is much lower than in the catalyst of example 1.
(3) The catalyst Pt/TiO obtained in this example 2 -1 catalytic activity test:
Pt/TiO at different temperatures 2 The change in catalytic activity of the catalyst (FIG. 17) shows that at high space velocity (800L g) cat -1 h -1 )，Pt/TiO 2 -1 catalyst completely degrading 120ppm formaldehyde to CO 2 And H 2 The reaction temperature of O is 40 ℃ which is far higher than the complete conversion temperature (20 ℃) of the catalyst of the example 1; in addition, the catalyst was used under room temperature (25 ℃) reaction conditionsThe mass ratio reaction rate was only 39.1. Mu. Mol g Pt -1 s -1 . Activity test conditions: the gas component is a mixture of 120ppm formaldehyde and synthetic air, and the gas space velocity is 800Lg cat -1 h -1 。
The embodiments described above are some of the embodiments of the present invention, but the embodiments of the present invention are not limited by the embodiments described above, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the supported noble metal formaldehyde removal catalyst with high-density synergistic catalytic active sites is characterized by comprising the following steps:
dissolving noble metal salt and/or noble metal acid and organic acid salt in a hydroxide aqueous solution to obtain a noble metal solution, adding a metal oxide carrier into the noble metal solution, stirring and impregnating, and evaporating and drying the noble metal salt and/or the noble metal acid and the organic acid salt by a solvent to obtain an impregnated sample; and carrying out reduction heat treatment on the impregnated sample to obtain the supported noble metal formaldehyde removal catalyst with high-density synergistic catalytic active sites.
2. The method for preparing a supported noble metal formaldehyde-removing catalyst with high-density synergistic catalytic active sites as claimed in claim 1, wherein the noble metal salt is sodium hexahydroxy platinate (IV) Na 2 [Pt(OH) 6 ]Potassium hexahydroxyplatinate (IV) K 2 [Pt(OH) 6 ]Sodium chloroplatinate Na 2 PtCl 6 Platinum nitrate Pt (NO) 3 ) 2 Platinum hydroxide Pt (OH) 4 Gold hydroxide Au (OH) 3 At least one of (a) and (b); the noble metal acid is hexahydroxyplatinic acid (IV) H 2 [Pt(OH) 6 ]Chloroplatinic acid H 2 PtCl 6 Chloroauric acid H 2 AuCl 4 At least one of (a) and (b); the organic acid salt refers to ammonium formate CH 5 NO 2 Ammonium acetate C 2 H 7 NO 2 Ammonium propionate C 3 H 9 NO 2 At least one of (a) and (b); the hydroxide refers to an alkali metal hydroxide.
3. The method of preparing a supported noble metal formaldehyde-removal catalyst having a high density of synergistic catalytic sites as claimed in claim 2, wherein the alkali metal hydroxide comprises at least one of LiOH, naOH, KOH, rbOH, csOH.
4. The method for preparing a supported noble metal formaldehyde-removing catalyst having a high-density synergistic catalytic active sites according to claim 1, wherein the total concentration of noble metal salts and/or noble metal acids in the noble metal solution is 0.2-100mM; the concentration of the organic acid salt in the noble metal solution is 0.2-200mM; OH in the noble metal solution - The concentration is 1 multiplied by 10 -4 -5×10 3 mM; the metal oxide carrier is TiO 2 、TiO 2 ·xH 2 O、Ti 2 O 3 、CeO 2 、MnO 2 、Fe 2 O 3 、Co 3 O 4 At least one of (a) and (b); the ratio of the mass of noble metal in the noble metal salt and/or noble metal acid to the mass of the metal oxide carrier is 0.1-5wt%.
5. The method for preparing a supported noble metal formaldehyde-removing catalyst having a high-density synergistic catalytic active site as claimed in claim 1, wherein the time of the impregnation and stirring is 0.1-5 hours.
6. The method for preparing a supported noble metal formaldehyde-removing catalyst with high-density synergistic catalytic active sites according to claim 1, wherein the atmosphere of the reduction heat treatment is 1% -100% of hydrogen/argon mixed gas, the temperature of the reduction heat treatment is 100-400 ℃, and the time of the reduction heat treatment is 0.5-5h.
7. The supported noble metal formaldehyde-removing catalyst with high-density synergistic catalytic active sites prepared by the preparation method of any one of claims 1 to 6, which is characterized by comprising a noble metal active phase and a metal oxide carrier phase with oxygen-enriched defects, wherein the noble metal active phase is distributed on the surface of the metal oxide carrier phase with oxygen-enriched defects in the form of dispersed nano particles.
8. The supported noble metal formaldehyde-removing catalyst having a high density of co-catalytically active sites of claim 7, wherein the co-catalytically active sites are close proximity regions of noble metal nanoparticles and oxygen defects in the metal oxide support; the noble metal is at least one of Pt and Au; the metal oxide carrier with oxygen-enriched defect is TiO 2 、TiO 2 ·xH 2 O、Ti 2 O 3 、CeO 2 、MnO 2 、Fe 2 O 3 、Co 3 O 4 At least one of them.
9. The supported noble metal formaldehyde-removing catalyst having high-density co-catalytic active sites of claim 7, wherein the nanoparticle size of the noble metal active phase is 0.2-3 nm.
10. Use of a supported noble metal formaldehyde-removing catalyst having a high density of synergistic catalytically active sites as claimed in any of claims 7 to 9 in the catalytic oxidation of formaldehyde.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111135822A (en) * | 2018-11-06 | 2020-05-12 | 中国科学院大连化学物理研究所 | Application of high-dispersion noble metal supported catalyst in hydrogenation of aromatic nitro compound |
| CN111389412A (en) * | 2020-03-04 | 2020-07-10 | 华南理工大学 | Supported noble metal catalyst based on carrier morphology modification and preparation and application thereof |
| CN112871202A (en) * | 2021-01-11 | 2021-06-01 | 宁波方太厨具有限公司 | Preparation method of catalyst for catalytic decomposition of formaldehyde |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111135822A (en) * | 2018-11-06 | 2020-05-12 | 中国科学院大连化学物理研究所 | Application of high-dispersion noble metal supported catalyst in hydrogenation of aromatic nitro compound |
| CN111389412A (en) * | 2020-03-04 | 2020-07-10 | 华南理工大学 | Supported noble metal catalyst based on carrier morphology modification and preparation and application thereof |
| CN112871202A (en) * | 2021-01-11 | 2021-06-01 | 宁波方太厨具有限公司 | Preparation method of catalyst for catalytic decomposition of formaldehyde |
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| MUHUA CHEN，ET AL.: "Identification of Active Sites in HCHO Oxidation over TiO2-Supported Pt Catalysts", 《ACS CATAL.》, vol. 12, no. 9, 25 April 2022 (2022-04-25), pages 5565 - 5573 * |
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