CN116836203A - Water-soluble Pt (IV) complex with hydroxycarboxylic acid as axial ligand, preparation method and application - Google Patents
Water-soluble Pt (IV) complex with hydroxycarboxylic acid as axial ligand, preparation method and application Download PDFInfo
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- CN116836203A CN116836203A CN202310783577.3A CN202310783577A CN116836203A CN 116836203 A CN116836203 A CN 116836203A CN 202310783577 A CN202310783577 A CN 202310783577A CN 116836203 A CN116836203 A CN 116836203A
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- hydroxycarboxylic acid
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003446 ligand Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-M 3-carboxy-2-(carboxymethyl)-2-hydroxypropanoate Chemical compound OC(=O)CC(O)(C(O)=O)CC([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-M 0.000 claims abstract description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-M L-tartrate(1-) Chemical compound OC(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-M 0.000 claims abstract description 3
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 3
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- 150000003893 lactate salts Chemical group 0.000 claims abstract 2
- 239000002243 precursor Substances 0.000 claims description 25
- 230000003197 catalytic effect Effects 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-M 3-carboxy-2,3-dihydroxypropanoate Chemical compound OC(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-M 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011591 potassium Substances 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 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 abstract description 5
- 229910052700 potassium Inorganic materials 0.000 abstract description 5
- 239000011734 sodium Substances 0.000 abstract description 5
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000460 chlorine Substances 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229940095064 tartrate Drugs 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 nitrogen oxide compound Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004376 petroleum reforming Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0086—Platinum compounds
- C07F15/0093—Platinum compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Abstract
The invention discloses a water-soluble Pt (IV) complex taking hydroxy carboxylic acid as an axial ligand, a preparation method and application thereof, and the molecular formula is trans- [ Pt (NH) 3 ) 4 (OH)(OOCR)](NO 3 ) 2 ( ‑ OOCR is lactate, hydrogen tartrate or dihydrogen citrate), that is, ammonia, hydroxy and hydroxycarboxylic acid are used as internal ligands to form hexacoordinated octahedral cation with Pt (iv), and 2 nitrate are used as external anions to play a role in charge balance. The synthesis is carried out by [ Pt (NH) 3 ) 4 ](NO 3 ) 2 To take the initiativeThe initial material is first axially oxidized with excessive hydrogen peroxide to form trans- [ Pt (NH) 3 ) 4 (OH) 2 ](NO 3 ) 2 Then carrying out axial neutralization reaction with equimolar quantity of hydroxycarboxylic acid to obtain the water-soluble target Pt (IV) complex. The synthesis method of the invention is simple, easy to control, high in yield and suitable for batch synthesis. The Pt (IV) complex does not contain chlorine, sulfur, phosphine, sodium, potassium and other elements harmful to the catalyst, has high water solubility, and can be used for producing industrial supported platinum catalysts.
Description
Technical Field
The invention relates to a water-soluble Pt (IV) complex trans- [ Pt (NH) with hydroxycarboxylic acid as an axial ligand 3 ) 4 (OH)(OOCR)](NO 3 ) 2 ( - OOCR is lactate, hydrogen tartrate or dihydrogen citrate), a preparation method and application thereof as a catalytic precursor, and belongs to the field of chemistry and chemical engineering.
Background
The supported platinum catalyst is a very important heterogeneous reaction catalyst, has the characteristics of excellent catalytic activity, strong selectivity, high stability, long catalytic life and the like, is an excellent catalyst for hydrogenation and dehydrogenation reactions, petroleum reforming reactions, oxidation reactions, cracking reactions, isomerization reactions, disproportionation reactions, decarboxylation reactions and deamination reactions, and is widely applied to the fields of inorganic chemical industry, organic chemical industry, fine chemical industry, petrochemical industry, environmental protection and environmental management, fuel cells and the like. Currently, the main technology for preparing supported platinum catalysts is a chemical impregnation method, one of the key steps is liquid phase loading, namely loading active components of the catalysts on a carrier material (gamma-Al 2 O 3 、SiO 2 、TiO 2 Activated carbon, etc.). The catalytic precursor is used as a main source of active ingredients of the supported platinum catalyst, the composition, the structure and the physical and chemical properties of the catalytic precursor have important influence on the performance of the prepared catalyst, and the requirements of the catalysts with different purposes on the composition and the structure of the precursor are different.
Currently, the industrially used platinum precursor is mainly chloroplatinic acid H 2 PtCl 6 And platinum nitrate Pt (NO) 3 ) 2 Solution (with 10% nitric acid). However, there are significant drawbacks to the use of both catalytic precursors. For example, when chloroplatinic acid is used as a precursor for preparing VOCs (volatile organic compounds) purification catalysts and automobile exhaust purification catalysts, chloride ions remained in the catalysts can obviously reduce the activity and the service life of the catalysts; when platinum nitrate is used as a precursor, the compound is unstable and only exists in more than 10% of nitric acid, the obtained impregnating solution is very acidic and can corrode the surface structure of a carrier, so that the performance of the catalyst is affected, and a large amount of nitrogen oxide compound gas is released in the calcining process of the catalyst preparation due to the existence of excessive nitric acid, so that the clean production is not facilitated. Meanwhile, research and application practices in academic and industrial fields prove that sulfur and phosphorus belong to elements toxic to metal catalysts, and the catalytic activity can be reduced; potassium and sodium ions migrate within the support and cause agglomeration of the active metal upon calcination, thereby reducing the dispersity and particle size of the active centers, and thus, the catalytic precursor compounds are required to be free of harmful elements such as sulfur, phosphorus, potassium, sodium, and the like.
Based on the requirements, it is of great importance to develop a platinum catalytic precursor compound which has high water solubility and does not contain harmful elements such as chlorine, sulfur, phosphorus, sodium, potassium and the like.
CN113278034A discloses a novel water-soluble Pt (IV) precursor compound trans- [ Pt (NH) 3 ) 4 (OH) 2 ](CH 3 COO) 2 And [ Pt (NH) 3 ) 5 (OH)](CH 3 COO) 3 Although the precursor compounds do not contain harmful elements such as chlorine, sulfur, phosphine, sodium, potassium and the like, the synthesis steps of the catalytic precursor compounds are complicated, and the batch synthesis is difficult.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects of the prior art, simplifying the synthesis steps, and providing a water-soluble Pt (IV) complex and a preparation method thereof, which are used for replacing a supported platinum catalyst prepared by using platinum nitrate (in 10% nitric acid solution) as a catalytic precursor in the industry at present.
For this purpose, the invention provides a water-soluble Pt (IV) complex trans- [ Pt (NH) with hydroxycarboxylic acid as axial ligand 3 ) 4 (OH)(OOCR)](NO 3 ) 2 ( - OOCR is lactate, bitartrate or dihydrogen citrate), ammonia, hydroxy and hydroxycarboxylic acid are used as internal ligands, hexa-coordination, octahedral cation with Pt (iv) is formed, and at the same time, the introduction of axial hydroxycarboxylic acid ligand also gives the whole complex high water solubility. Nitrate is taken as external anions to play a role in charge balance. Such complex molecules, depending on the synthesis conditions, generally contain 0 to 2 crystal waters.
The water-soluble Pt (IV) complex trans- [ Pt (NH) with hydroxycarboxylic acid as axial ligand 3 ) 4 (OH)OOCR)](NO 3 ) 2 The chemical structural formula is as follows:
the water-soluble Pt (IV) complex trans- [ Pt (NH) 3 ) 4 (OH)(OOCR)](NO 3 ) 2 The preparation method of (2) comprises the following steps:
in the form of a commercially available Pt (II) complex [ Pt (NH) 3 ) 4 ](NO 3 ) 2 As a starting material, an excess of 30wt.% hydrogen peroxide was added for axial oxidation to a water-less trans- [ Pt (NH) 3 ) 4 (OH) 2 ](NO 3 ) 2 Then interact with equimolar amount of hydroxy carboxylic acid (lactic acid, tartaric acid, citric acid) to perform axial neutralization reaction to obtain water-soluble target complex trans- [ Pt (NH) 3 ) 4 (OH)(OOCR)](NO 3 ) 2 The reaction scheme involved is as follows:
in addition, in trans- [ Pt (NH) 3 ) 4 (OH) 2 ](NO 3 ) 2 In the aqueous solution system of the reaction with the hydroxycarboxylic acid, no matter how the reaction conditions are enhanced (such as increasing the dosage of the hydroxycarboxylic acid, increasing the reaction temperature, etc.), the hydroxycarboxylic acid can only replace 1 hydroxyl ligand therein, and trans- [ Pt (NH) generated by replacing 2 hydroxyl ligands with 2 hydroxycarboxylic acids is not obtained 3 ) 4 (OOCR) 2 ](NO 3 ) 2 The structural formula is as follows:
compared with the prior art, the Pt (IV) complex has the following characteristics:
(1) The catalyst does not contain elements harmful to the catalyst, such as chlorine, sulfur, phosphorus, sodium, potassium and the like, and does not have adverse effect on the catalytic performance of the catalyst.
(2) Has high water solubility, the solubility in water at room temperature is up to more than 100g/L, and the water is stable, and insoluble substances can not be decomposed when the water is heated to boiling.
(3) Belongs to ionic compounds. The dissociation reaction takes place in the aqueous solution, and the stable cation-complex trans- [ Pt (NH) 3 ) 4 (OOCR) 2 ] 2+ Can be effectively and physically adsorbed on the surface of negatively charged carrier, such as gamma-Al 2 O 3 And modifying active carbon, and the like, and simultaneously, hydroxyl and carboxyl groups carried by the axial hydroxycarboxylic acid ligand can be chemically bonded with carboxyl or hydroxyl groups on the surface of the carrier, so that the precursor is directionally anchored on the surface of the carrier, which is beneficial to the loading procedure of catalyst preparation.
(4) The synthetic process route is short, the yield is high, and the cost is relatively low.
(5) With trans- [ Pt (NH) 3 ) 4 (OH)(OOCR)](NO 3 ) 2 Instead of the platinum nitrate (in 10% nitric acid solution) which is currently used in industry as a catalytic precursor, a chemical impregnation method is adopted to prepare a platinum catalyst for purifying VOCs, and the catalytic conversion performance of the platinum catalyst for purifying VOCs on common representative organic volatile gas diethyl carbonate (DEC) is tested. The results show that: catalyst Pt/Al prepared by adopting Pt (IV) complex of the invention 2 O 3 The ignition temperature and the conversion rate of the catalyst to DEC are superior to those of the similar catalyst prepared by taking platinum nitrate as a catalytic precursor.
Drawings
FIG. 1 is a graph showing the light-off characteristics of a catalyst prepared from 3 Pt (IV) complexes prepared in accordance with an example of the present invention and commercially available platinum nitrate as precursors for catalytic oxidation of DEC.
Detailed Description
Example 1 intermediate trans- [ Pt (NH) 3 ) 4 (OH) 2 ](NO 3 ) 2 Is prepared from
Will [ Pt (NH) 3 ) 4 ](NO 3 ) 2 (100.00 g,258.40 mmol) is dissolved in 300mL of water, 30wt.% hydrogen peroxide (340 mL) is added dropwise under the condition of heating and stirring at 60 ℃, a large amount of white solid is precipitated during the dripping process, the heating and stirring reaction is continued for 4 hours after the dripping is finished, the mixture is cooled to room temperature overnight, filtered, washed with ice water for 3 times, with ice absolute ethanol for 1 time in sequence, and dried to obtain 100.50g of trans- [ Pt (NH) 3 ) 4 (OH) 2 ](NO 3 ) 2 The yield was 92.39%.
Structural feature parameters:
<1> elemental analysis: measurement values Pt 45.88%, H4.29%, N19.18% (calculated values Pt 46.31%, H3.33%, N19.95%).
Example 2 trans- [ Pt (NH) 3 ) 4 (OH)(OOCCH(OH)CH 3 )](NO 3 ) 2 ·2H 2 Synthesis of O
Lactic acid (1.89 g,21.00 mmol) was added to trans- [ Pt (NH) 3 ) 4 (OH) 2 ](NO 3 ) 2 (8.03 g,19.07 mmol) in water (65 mL), stirring at 70-150 ℃ for 24 hours, and completely dissolving the solid to obtainThe pale yellow clear solution was distilled to near dryness under reduced pressure to give a white solid residue, which was collected by filtration, washed 3 times with ice absolute ethanol, and dried to give 9.31g of trans- [ Pt (NH) 3 ) 4 (OH)(OOCCH(OH)CH 3 )](NO 3 ) 2 ·2H 2 O, yield 92.26%.
Structural feature parameters:
<1> elemental analysis: measurement values Pt 36.69%, C6.05%, H4.99%, N15.24% (calculated values Pt 36.86%, C6.81%, H4.16%, N15.88%);
<2> 1 H NMR(500MHz,DMSO-d 6 )δ6.18-5.40(m,12H,4NH 3 ),4.78(d,J=5.2Hz,1H,OH-lactate),4.50(d,J=5.0Hz,1H,CH-lactate),4.15-3.99(m,1H,OH-Pt),3.35(s,H 2 O),2.50(p,J=1.8Hz,DMSO),1.22(t,J=7.2Hz,3H,CH 3 -lactate);
<3> 13 C NMR(126MHz,DMSO-d 6 )δ181.32,66.77,39.52(dp,J=42.0,21.0Hz,DMSO),21.07;
<4>3400(m),3203(m),1650(s),1383(s),590(w),535(w);
<5>FAB + -MS:368[M-2H 2 O-2NO 3 -H] + ,261[M-2H 2 O-2NO 3 -NH 3 -lactate-2H] + ,185[M-2H 2 O-2NO 3 ] 2+ 。
example 3 trans- [ Pt (NH) 3 ) 4 (OH)(OOCCH(OH)CH(OH)COOH)](NO 3 ) 2 Is synthesized by (a)
Tartaric acid (2.77 g,18.59 mmol) was dissolved in 25mL of water and trans- [ Pt (NH) 3 ) 4 (OH) 2 ](NO 3 ) 2 (7.07 g,16.79 mmol) in water (40 mL) and stirring at 70-150 ℃ for 24 hours, then completely dissolving the solid to obtain a yellow clear solution, decompressing and steaming the solution until the solution is nearly dry to obtain yellow oily residue, adding a large amount of ice absolute ethyl alcohol to separate out pale yellow solid, filtering and collecting, washing with ice absolute ethyl alcohol for 3 times, and drying to obtain 8.50gtrans- [ Pt (NH) 3 ) 4 (OH)(OOCCH(OH)CH(OH)COOH)](NO 3 ) 2 The yield was 91.53%。
Structural feature parameters:
<1> elemental analysis: measurement values Pt 35.65%, C8.07%, H3.98%, N14.76% (calculated values Pt 35.26%, C8.68%, H3.25%, N15.19%);
<2> 1 H NMR(500MHz,DMSO-d 6 )δ6.50-5.41(m,12H,4NH 3 ),4.40(d,J=14.7Hz,1H,CH-tartrate),4.27(s,1H,CH-tartrate),4.09(s,OH-Pt,OH-tartrate,H 2 O),2.50(s,DMSO);
<3> 13 C NMR(126MHz,DMSO-d 6 )δ178.18,173.48,73.08,72.24,39.52(dp,J=42.0,21.1Hz,DMSO);
<4>3375(m),3241(m),1678(s),1384(s),590(w),511(w);
<5>FAB + -MS:261[M-2NO 3 -NH 3 -tartrate-2H] + 。
example 4 trans- [ Pt (NH) 3 ) 4 (OH)(OOCC(OH)(CH 2 COOH) 2 )](NO 3 ) 2 ·2H 2 Synthesis of O
Citric acid (3.57 g,18.59 mmol) was dissolved in 50mL of water and trans- [ Pt (NH) 3 ) 4 (OH) 2 ](NO 3 ) 2 (7.11 g,16.89 mmol) in water (50 mL) and stirring at 70-150 ℃ for 24 hours to obtain a pale yellow clear solution, the solution is decompressed and distilled to near dryness to obtain a pale yellow oily residue, a large amount of ice absolute ethyl alcohol is added to separate out white solid, the white solid is filtered and collected, and washed 3 times with ice absolute ethyl alcohol, and the solution is dried to obtain 9.62gtrans- [ Pt (NH) 3 ) 4 (OH)(OOCC(OH)(CH 2 COOH) 2 )](NO 3 ) 2 ·2H 2 O, yield 90.27%.
Structural feature parameters:
<1> elemental analysis: measurement values Pt 30.74%, C10.95%, H4.67%, N13.10% (calculated values Pt 30.90%, C11.41%, H3.80%, N13.31%);
<2> 1 H NMR(500MHz,DMSO-d 6 )δ5.66(d,J=36.5Hz,4NH 3 ),4.08(s,OH-Pt),3.49-3.40(m,1H,OH-citrate),3.35(s,H 2 O),2.83-2.52(m,4H,CH 2 -citrate),2.50(p,J=1.8Hz,DMSO);
<3> 13 C NMR(126MHz,DMSO-d 6 )δ180.76,176.73,171.94,73.39,45.53,43.25,39.52(dp,J=41.8,20.9Hz,DMSO);
<4>3426(m),3202(m),1717(s),1384(s),592(w),548(w);
<5>FAB + -MS:470[M-2H 2 O-2NO 3 -H] + ,453[M-2H 2 O-2NO 3 -NH 3 -H] + ,436[M-2H 2 O-2NO 3 -2NH 3 -H] + ,261[M-2H 2 O-2NO 3 -NH 3 -citrate-2H] + 。
example 5 VOCs purification catalyst and Performance evaluation prepared with the Pt (IV) Complex of the present invention as a precursor
Alumina is selected as a carrier, and the platinum nitrate (in the form of 10 percent nitric acid solution) and 3 Pt (IV) complexes of the invention, namely, the rans- [ Pt (NH) 3 ) 4 (OH)(OOCCH(OH)CH 3 )](NO 3 ) 2 ·2H 2 O、trans-[Pt(NH 3 ) 4 (OH)(OOCCH(OH)CH(OH)COOH)](NO 3 ) 2 And trans- [ Pt (NH) 3 ) 4 (OH)(OOCC(OH)(CH 2 COOH) 2 )](NO 3 ) 2 ·2H 2 O is used as a precursor, 4 catalysts containing platinum are prepared by adopting the same impregnation method and impregnation conditions, and the numbers are respectively: pt-N (control catalyst), pt (IV) -LN, pt (IV) -TN, and Pt-CN. Wherein the platinum loading is 0.3wt.%, the fresh sample (fresh) firing condition is 550 ℃,3h, ensuring complete decomposition of the noble metal precursor.
Adopting a normal pressure multifunctional micro fixed bed reaction device, and the airspeed Sv is 30000+/-500 h -1 The total flow was 6.0L/min and the specific test conditions are set forth in Table 1.
TABLE 1 catalyst Performance test conditions
After about 0.50g of a catalyst sample and 4.50g of quartz sand were mixed, the mixture was packed in a reaction tube having an inner diameter of 5mm, and the conversion efficiency, light-off temperature and complete conversion temperature of the catalyst for deep DEC oxidation in a continuous temperature increase test were examined by a chromatograph from the company fuli.
Continuous temperature rise test: heating from 100deg.C to 350deg.C for 250min.
The catalytic conversion performance of the 4 platinum catalysts on diethyl carbonate (DEC) is shown in fig. 1 and the relevant data are presented in table 2.
TABLE 2 catalytic Performance data for VOCs catalysts prepared from different precursors
T from FIGS. 1 and 2 50 And T 90 It can be seen that in a fresh state, the two catalysts of Pt (IV) -TN and Pt (IV) -CN prepared by the precursor have the same ignition property to DEC as Pt-N, and the Pt (IV) -LN is slightly worse; but the three pairs of DEC T 50 And T 90 Are all superior to Pt-N. Therefore, the Pt (IV) complex provided by the invention is used as a catalytic precursor, so that the VOCs purifying catalyst with excellent performance can be prepared, and the application prospect is good.
Claims (3)
1. A water-soluble Pt (IV) complex taking hydroxycarboxylic acid as an axial ligand is characterized in that:
trans- [ Pt (NH) 3 ) 4 (OH)(OOCR)](NO 3 ) 2 4 ammonia, 1 hydroxyl and 1 hydroxycarboxylic acid are used as internal ligand of Pt (IV) to form hexacoordinated octahedral coordination cation, and 2 nitrate are used as external anions;
wherein: OOCR is lactate, bitartrate or dihydrogen citrate, trans-means that the hydroxy and hydroxycarboxylic acid ligands are in the inversion position;
the chemical structural formula is as follows:
2. a method of preparing a water-soluble Pt (IV) complex having a hydroxycarboxylic acid as the axial ligand as claimed in claim 1, comprising:
with Pt (II) complexes [ Pt (NH) 3 ) 4 ](NO 3 ) 2 As a starting material, an excess of 30wt.% hydrogen peroxide was added for axial oxidation to a water-less trans- [ Pt (NH) 3 ) 4 (OH) 2 ](NO 3 ) 2 Then interact with equimolar amount of hydroxycarboxylic acid to perform axial neutralization reaction to obtain water-soluble target complex trans- [ Pt (NH) 3 ) 4 (OH)(OOCR)](NO 3 ) 2 The method comprises the steps of carrying out a first treatment on the surface of the The hydroxycarboxylic acid includes lactate, hydrogen tartrate or dihydrogen citrate;
the reaction route is as follows:
3. use of a water-soluble Pt (IV) complex with hydroxycarboxylic acid as axial ligand as claimed in claim 1 as catalytic precursor for the preparation of supported platinum catalysts.
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