CN116603521B - Cerium-zirconium oxide supported palladium-gold catalyst and preparation method and application thereof - Google Patents
Cerium-zirconium oxide supported palladium-gold catalyst and preparation method and application thereof Download PDFInfo
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- CN116603521B CN116603521B CN202310585960.8A CN202310585960A CN116603521B CN 116603521 B CN116603521 B CN 116603521B CN 202310585960 A CN202310585960 A CN 202310585960A CN 116603521 B CN116603521 B CN 116603521B
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- QWDUNBOWGVRUCG-UHFFFAOYSA-N n-(4-chloro-2-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1[N+]([O-])=O QWDUNBOWGVRUCG-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000010931 gold Substances 0.000 title claims abstract description 78
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 126
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 104
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000000243 solution Substances 0.000 claims abstract description 75
- 239000001257 hydrogen Substances 0.000 claims abstract description 59
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 59
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 150000002940 palladium Chemical class 0.000 claims abstract description 42
- 239000012266 salt solution Substances 0.000 claims abstract description 42
- 238000005530 etching Methods 0.000 claims abstract description 41
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 40
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000019253 formic acid Nutrition 0.000 claims abstract description 40
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000006185 dispersion Substances 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 19
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 38
- 239000002253 acid Substances 0.000 claims description 34
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 27
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 239000012279 sodium borohydride Substances 0.000 claims description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 11
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 23
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 31
- 229910021641 deionized water Inorganic materials 0.000 description 31
- 238000005406 washing Methods 0.000 description 29
- 238000001035 drying Methods 0.000 description 27
- 239000000839 emulsion Substances 0.000 description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 description 12
- 239000011550 stock solution Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 229910000420 cerium oxide Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 6
- 208000001408 Carbon monoxide poisoning Diseases 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 239000004280 Sodium formate Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 4
- 235000019254 sodium formate Nutrition 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 208000005374 Poisoning Diseases 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 palladium ions Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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Abstract
The invention relates to a cerium-zirconium oxide supported palladium-gold catalyst and a preparation method and application thereof, and belongs to the technical field of catalysts. The method comprises the following steps: uniformly mixing cerium nitrate hexahydrate and zirconyl nitrate hydrate, adding sodium hydroxide solution for hydrothermal reaction to obtain oxide, and calcining to obtain cerium zirconium oxide; dispersing a palladium salt solution into a palladium salt dispersion liquid by using water, then adding cerium-zirconium oxide, stirring, and then adding a reducing agent for reduction to obtain a cerium-zirconium oxide supported palladium composite material; adding a cerium-zirconium oxide supported palladium composite material and a precipitant into the gold salt solution for reaction to obtain the cerium-zirconium oxide supported palladium-gold composite material; and placing the cerium-zirconium oxide supported palladium-gold composite material into an etching solution for etching to prepare the cerium-zirconium oxide supported palladium-gold catalyst. The catalyst prepared by the invention can effectively resist CO poisoning, the catalytic activity of hydrogen production by formic acid is obviously improved, and the service life, stability and catalytic efficiency of the catalyst are improved.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a cerium-zirconium oxide supported palladium-gold catalyst, and a preparation method and application thereof.
Background
With the rapid development of sustainable clean energy, the conversion of these large-scale intermittent energy sources into green hydrogen can reduce the dependence on fossil energy sources, thereby realizing carbon neutralization society. And then, the hydrogen is extremely challenging to store and transport on a large scale due to the physicochemical properties of ultralow density, difficult liquefaction, explosiveness and the like. Among a plurality of hydrogen storage paths, the normal-temperature normal-pressure organic liquid hydrogen storage has the characteristics of safety, high hydrogen storage density, complete infrastructure and the like, and is widely paid attention to. Among them, formic acid has a hydrogen storage density of 53g/L and higher than 35MPa in a high-pressure hydrogen storage tank, and can be safely prepared and transported in a large scale, so that the hydrogen production by hydrogen storage of formic acid is an important chemical approach in the future. The principle of hydrogen production from formic acid is that formic acid can produce hydrogen and carbon dioxide through dehydrogenation reaction under the action of a catalyst, and byproducts such as carbon monoxide can be produced. At present, the traditional formic acid hydrogen production catalyst has the problems of low catalytic efficiency, poor stability and the like, so that the large-scale commercial application of the formic acid hydrogen production is limited. Therefore, the research and development of the catalyst with high efficiency, stability and good selectivity become a hot spot for the research of hydrogen production of formic acid.
Palladium is one of the catalysts commonly used in the dehydrogenation of formic acid, and has high catalytic activity and good hydrogen selectivity. However, single palladium-based heterogeneous catalysts have the problems of easy aggregation, low stability, inactivation and the like, and limit the application of the single palladium-based heterogeneous catalysts in hydrogen production from formic acid. In order to overcome these problems, supported palladium-based catalysts, such as palladium-based catalysts in which the carrier is a carbon material, oxide-supported palladium-based catalysts, and the like, have been developed.
Among these catalysts, ceria has been attracting attention as a typical support material due to its high specific surface area, high oxygen storage vacancy capacity and good catalytic performance. However, the activity and stability of the ceria support need to be further improved due to the acidic environment of hydrogen production from formic acid. In addition, in the path of the hydrogen production reaction of formic acid, a small amount of carbon monoxide is always generated, and the carbon monoxide generated in situ can be adsorbed and coordinated on the surface of palladium active sites, so that the selectivity and the activity of the catalyst are greatly reduced. It is supposed that the palladium-based hydrogen production catalyst with stable carrier and carbon monoxide poisoning resistance is of great significance to the commercial application of formic acid hydrogen storage scale.
Disclosure of Invention
In order to solve one or more technical problems in the prior art, the invention provides a cerium-zirconium oxide supported palladium-gold catalyst, and a preparation method and application thereof. The invention prepares the stable cerium-zirconium oxide supported bifunctional composite site palladium-gold formic acid hydrogen production catalyst, the introduction of zirconium enables the corrosion resistance of cerium oxide to be improved, and the oxygen storage vacancy capacity to be promoted, and due to the inclusion of the palladium-gold bifunctional active site, the catalytic activity of the formic acid hydrogen production catalyst can be cooperatively improved, and meanwhile, the stability of the catalyst can be improved by utilizing the carbon monoxide (CO) poisoning resistance characteristic of gold, so that the catalytic efficiency of formic acid hydrogen production is improved.
The invention provides a preparation method of a cerium-zirconium oxide supported palladium-gold catalyst in a first aspect, which comprises the following steps:
(1) Uniformly mixing cerium nitrate hexahydrate and zirconium oxynitrate hydrate with water to obtain a mixed solution, adding sodium hydroxide solution into the mixed solution for hydrothermal reaction to obtain an oxide, and calcining the oxide to obtain cerium zirconium oxide;
(2) Dispersing a palladium salt solution into a palladium salt dispersion liquid by using water, adding cerium-zirconium oxide into the palladium salt dispersion liquid, stirring, and adding a reducing agent for reduction to obtain a cerium-zirconium oxide supported palladium composite material;
(3) Adding a cerium-zirconium oxide supported palladium composite material and urea into the gold salt solution to react to obtain the cerium-zirconium oxide supported palladium-gold composite material;
(4) And placing the cerium-zirconium oxide supported palladium-gold composite material into an etching solution for etching to prepare the cerium-zirconium oxide supported palladium-gold catalyst.
Preferably, in step (1): the molar ratio of the cerium nitrate hexahydrate to the amount of the zirconyl nitrate hydrate is (1-3): (1-3); the mixed solution contains 20-40% of cerium nitrate hexahydrate and zirconyl nitrate hydrate by mass percent; the concentration of the sodium hydroxide solution is 8-12 mol/L; the volume ratio of the mixed solution to the sodium hydroxide solution is 1: (1-2); the temperature of the hydrothermal reaction is 150-200 ℃, and the time of the hydrothermal reaction is 12-24 hours; the calcination is performed in an air atmosphere; and/or the calcining temperature is 400-800 ℃, and the calcining time is 4-8 hours.
Preferably, in step (2): the palladium salt solution is a palladium chloride acid solution, the palladium chloride acid solution is prepared from hydrochloric acid with the pH value of 0-2 and palladium dichloride, and the concentration of the palladium dichloride in the palladium chloride acid solution is 0.05-0.15 mol/L; and/or the volume ratio of the water to the palladium salt solution is (50-80): 1.
preferably, in step (2): the mass ratio of the cerium zirconium oxide to the reducing agent is (130-150): 1, a step of; the molar ratio of palladium contained in the palladium salt solution to the reducing agent is 1: (3-12); the reducing agent is one or more of sodium borohydride, potassium borohydride and hydrazine hydrate; the stirring time is 6-15 h, and the stirring rotating speed is 300-800 r/min; and/or the reduction time is 0.5-2 h.
Preferably, in step (3): the gold salt solution is chloroauric acid aqueous solution, and the concentration of the chloroauric acid aqueous solution is 0.00002-0.00004 mol/L; and/or the reaction is to heat treat at 80-100 ℃ for 6-10 hours and then age at 15-35 ℃ for 10-15 hours.
Preferably, the molar ratio of palladium contained in the palladium salt solution to gold contained in the gold salt solution is (10 to 35): 1, a step of; and/or the molar ratio of gold contained in the gold salt solution to urea is 1: (110-140).
Preferably, in step (4): the etching solution is an etchant aqueous solution with pH of 11-13; the etchant contained in the etchant aqueous solution is sodium cyanide and/or sodium cyanate; the etchant aqueous solution contains 1-3% of etchant by mass.
Preferably, the etching temperature is 15-35 ℃, and the etching time is 5-120 min.
The present invention provides in a second aspect a cerium zirconium oxide supported palladium gold catalyst prepared by the preparation method of the present invention described in the first aspect.
The invention provides in a third aspect the use of a cerium zirconium oxide supported palladium gold catalyst prepared by the preparation method of the invention in the first aspect in hydrogen production from formic acid.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The cerium-zirconium oxide supported palladium-gold catalyst prepared by the invention is a cerium-zirconium oxide supported difunctional composite site palladium-gold formic acid hydrogen production catalyst, and adopts metal zirconium to improve the corrosion resistance of cerium oxide and the capability of the cerium oxide to store oxygen vacancies at the same time, and the zirconium doped cerium oxide material (cerium-zirconium oxide Ce x Zr y O 2 ) The oxygen vacancy ability and corrosion resistance of the carrier material can be simultaneously improved, and the activity and stability of the carrier are improved, so that the catalytic activity and stability of the formic acid hydrogen production catalyst can be improved.
(2) The invention adopts two metals of palladium and gold as double-function composite sites, and the catalytic activity of the formic acid hydrogen production catalyst is obviously improved due to the two active sites of palladium and gold, and the introduction of the active site of gold can be used as scavenger of carbon monoxide to oxidize adsorption state carbon monoxide, thereby effectively resisting carbon monoxide poisoning and improving the stability, service life and catalytic efficiency of the formic acid hydrogen production catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a cerium-zirconium oxide supported palladium-gold catalyst in a first aspect, which comprises the following steps:
(1) Mixing cerium nitrate hexahydrate and zirconium oxynitrate hydrate with water to obtain mixed solution, adding sodium hydroxide solution into the mixed solution to make hydrothermal reaction to obtain oxide, and calcining the oxide to obtain the invented productCerium zirconium oxide Ce x Zr y O 2 Wherein x+y=1, and 0 < y < 1; in the invention, cerium nitrate hexahydrate is used as a cerium source, zirconium oxynitrate hydrate is used as a zirconium source, and the cerium zirconium oxide Ce is obtained through hydrothermal reaction and calcination x Zr y O 2 By adjusting the molar ratio of the cerium source and the zirconium source, the cerium-zirconium oxide Ce with different values of x and y can be obtained x Zr y O 2 In the present invention, it is preferable that 0.25.ltoreq.y.ltoreq.0.75; in some specific embodiments, cerium nitrate hexahydrate and zirconium oxynitrate hydrate are uniformly mixed with water to obtain a mixed solution, then a sodium hydroxide solution is added into the mixed solution, stirring is carried out for 20-40 min at the room temperature of 15-35 ℃ and the rotating speed of 300-800 r/min to obtain an emulsion, the emulsion is subjected to hydrothermal reaction to obtain an oxide, and the oxide is calcined to obtain cerium zirconium oxide Ce x Zr y O 2 In the invention, after emulsion is formed, hydrothermal reaction is carried out, so that the effect of nucleation and crystal growth is achieved; in the invention, for example, after the hydrothermal reaction is finished, the obtained oxide is washed and dried and then calcined, preferably, before the calcination, the oxide is centrifugally washed and then is dried for 8-18 hours at 40-80 ℃, and the centrifugal washing can be carried out for example by adopting deionized water for centrifugal washing for 4-8 times;
(2) Dispersing a palladium salt solution into a palladium salt dispersion liquid by using water, adding cerium-zirconium oxide into the palladium salt dispersion liquid, stirring, and adding a reducing agent for reduction to obtain a cerium-zirconium oxide supported palladium composite material; the invention does not limit the dosage of each component in the step (2), and can be adjusted according to the loading capacity of the palladium nano particles; in the invention, after reduction is finished, centrifugal washing and drying (for example, drying at 40-80 ℃) are carried out, so that the cerium-zirconium oxide supported palladium composite material is obtained; in the step (2) of the present invention, the stirring and/or the reduction may be performed, for example, at a room temperature of 15 to 35 ℃ and a rotational speed of 300 to 800r/min, the stirring time may be, for example, 6 to 15 hours, and the reduction time may be, for example, 0.5 to 2 hours;
(3) Adding a cerium-zirconium oxide supported palladium composite material and urea into the gold salt solution to react to obtain the cerium-zirconium oxide supported palladium-gold composite material;
(4) Placing the cerium-zirconium oxide supported palladium-gold composite material into an etching solution to etch (gold etching) to prepare a cerium-zirconium oxide supported palladium-gold catalyst; in the invention, the etching temperature and time are adjustable; in the invention, the cerium-zirconium oxide loaded palladium-gold composite material is placed in an etching solution to etch gold, and gold attached to the surface of the cerium-zirconium oxide is etched, so that gold nanoclusters can be generated, more catalytic active sites can be provided, the catalytic activity can be effectively improved, and the control of the reaction selectivity can be realized, so that the catalyst shows good hydrogen selectivity; in addition, the high-energy sites on the surface of the gold nanoclusters have higher electron affinity, and can better adsorb and stabilize toxic substances, so that the antitoxic performance of the catalyst is effectively improved, and the stability and the service life of the formic acid hydrogen production catalyst are improved.
The invention firstly utilizes a synthesized zirconium-doped cerium oxide material (cerium zirconium oxide Ce) x Zr y O 2 ) The oxygen vacancy ability and corrosion resistance of the carrier material can be simultaneously improved, and the activity and stability of the carrier are improved; secondly, gold and palladium are supported to generate a dual-function composite site, a large amount of palladium ions are adsorbed on the surface of the catalyst through palladium salt solution, palladium ions are reduced into palladium particles through reducing agent, urea is used for treatment in dispersed gold salt solution, and finally gold etching reaction is carried out in etching solution to prepare the cerium-zirconium oxide supported palladium-gold catalyst, so that the catalytic performance of the catalyst is greatly improved, the selectivity of the catalyst in formic acid dehydrogenation reaction is improved, the carbon monoxide (CO) poisoning resistance is improved, and the stability and the service life of the formic acid hydrogen production catalyst are improved; by adopting a double-functional site design, a gold (Au) nano heterojunction material is introduced, and meanwhile, the activity and carbon monoxide poisoning resistance of the catalyst are improved.
According to some preferred embodiments, in step (1): the molar ratio of the cerium nitrate hexahydrate to the amount of the zirconyl nitrate hydrate is (1-3): (1-3) (e.g., 1:1, 1:2, 1:3, 2:1, or 3:1), preferably (1-3): 1, more preferably 3:1; in the present invention, the molar ratio of the cerium nitrate hexahydrate to the zirconyl nitrate hydrate is preferably (1 to 3): (1-3), if the dosage of cerium nitrate hexahydrate or zirconium oxynitrate hydrate is too much or too little, the activity and stability of the obtained cerium zirconium oxide serving as a carrier can be influenced, so that the catalytic activity and stability of the prepared cerium zirconium oxide supported palladium gold catalyst are influenced; the mixed solution contains 20-40% of cerium nitrate hexahydrate and zirconyl nitrate hydrate (for example, 20%, 25%, 30%, 35% or 40%); the concentration of the sodium hydroxide solution is 8-12 mol/L (for example, 8, 9, 10, 11 or 12 mol/L); in the present invention, the sodium hydroxide solution refers to an aqueous sodium hydroxide solution unless otherwise specified; the volume ratio of the mixed solution to the sodium hydroxide solution is 1: (1-2) (e.g., 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, or 1:2); the temperature of the hydrothermal reaction is 150-200 ℃ (e.g. 150 ℃, 160 ℃, 180 ℃, 190 ℃ or 200 ℃), and the time of the hydrothermal reaction is 12-24 hours (e.g. 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24 hours); the calcination is performed in an air atmosphere; and/or the calcination temperature is 400-800 ℃ (e.g. 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ or 800 ℃), and the calcination time is 4-8 hours (e.g. 4, 5, 6, 7 or 8 hours).
According to some preferred embodiments, in step (2): the palladium salt solution is a palladium chloride acid solution, the palladium chloride acid solution is prepared from hydrochloric acid with the pH value of 0-2 and palladium dichloride, and the concentration of the palladium dichloride contained in the palladium chloride acid solution is 0.05-0.15 mol/L (for example, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14 or 0.15 mol/L); and/or the volume ratio of the water to the palladium salt solution is (50-80): 1 (e.g., 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, or 80:1).
According to some preferred embodiments, in step (2): the mass ratio of the cerium zirconium oxide to the reducing agent is (130-150): 1 (e.g., 130:1, 135:1, 140:1, 145:1, or 150:1); the molar ratio of palladium contained in the palladium salt solution to the reducing agent is 1: (3-12) (e.g., 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, 1:10.5, 1:11, 1:11.5, or 1:12); the reducing agent is one or more of sodium borohydride, potassium borohydride and hydrazine hydrate; the stirring time is 6-15 h (for example, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 h), and the stirring rotating speed is 300-800 r/min (for example, 300, 400, 500, 600, 700 or 800 r/min); and/or the time of the reduction is 0.5-2 hours (e.g., 0.5, 1, 1.5 or 2 hours).
According to some preferred embodiments, in step (3): the gold salt solution is chloroauric acid aqueous solution, and the concentration of the chloroauric acid aqueous solution is 0.00002-0.00004 mol/L (for example, 0.00002, 0.00003 or 0.00004 mol/L); and/or the reaction is to heat treat at 80-100 ℃ (e.g. 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃) for 6-10 hours (e.g. 6, 7, 8, 9 or 10 hours), and then age at 15-35 ℃ (e.g. 15 ℃, 20 ℃, 25 ℃, 30 ℃ or 35 ℃) for 10-15 hours (e.g. 10, 11, 12, 13, 14 or 15 hours).
According to some preferred embodiments, the molar ratio of palladium contained in the palladium salt solution to gold contained in the gold salt solution is (10 to 35): 1 (e.g., 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 25:1, 30:1, or 35:1); in the present invention, it is preferable that the molar ratio of palladium contained in the palladium salt solution to gold contained in the gold salt solution is (10 to 35): and 1, the cerium-zirconium oxide supported palladium-gold catalyst with better palladium-gold double-functional site composite effect can be obtained, so that the catalytic activity, the catalytic stability and the like of the cerium-zirconium oxide supported palladium-gold catalyst are improved.
According to some preferred embodiments, the molar ratio of gold contained in the gold salt solution to urea is 1: (110-140) (e.g., 1:110, 1:115, 1:120, 1:125, 1:130, 1:135, or 1:140), preferably 1:125.
According to some preferred embodiments, in step (4): the etching solution is an etchant aqueous solution with pH of 11-13; the etchant contained in the etchant aqueous solution is sodium cyanide and/or sodium cyanate; the etchant aqueous solution contains 1-3% of etchant (for example, 1%, 1.5%, 2%, 2.5% or 3%); in the present invention, for example, an alkaline regulator (such as sodium hydroxide and/or potassium hydroxide) may be used to adjust the pH of the aqueous etchant solution to 11-13, preferably to 12, where the alkaline regulator may be directly added to the aqueous etchant solution, or added to the aqueous etchant solution in the form of an aqueous solution, and the concentration of the aqueous alkaline regulator is, for example, 0.05-0.2 mol/L, and the amount of the alkaline regulator or the aqueous alkaline regulator is not specifically limited, so that the pH of the aqueous etchant solution may be 11-13; the invention does not limit the dosage of the etching solution, and can ensure that the cerium-zirconium oxide loaded palladium-gold composite material is completely immersed in the etching solution.
According to some preferred embodiments, in step (4): the etching temperature is 15-35 ℃, and the etching time is 5-120 min; in the invention, the etching time can be adjusted according to the concentration of the etchant solution, the gold loading capacity and the like, preferably the etching time is 5-120 min, more preferably the etching time is 5-20 min.
According to some specific embodiments, the preparation of the cerium zirconium oxide supported palladium gold catalyst comprises the following steps:
(1) uniformly mixing cerium nitrate hexahydrate and zirconium oxynitrate hydrate with deionized water to obtain a mixed solution, dissolving flaky sodium hydroxide in deionized water to obtain a sodium hydroxide aqueous solution, adding the sodium hydroxide solution into the mixed solution, stirring for 20-40 min at the temperature of 15-35 ℃ and the rotating speed of 300-800 r/min to obtain an emulsion, transferring the emulsion into a hydrothermal reaction kettle for hydrothermal reaction, and after the reaction is finished, performing centrifugal washing and drying to obtain an oxide, wherein the centrifugal washing is performed by using deionized water for centrifugal washing6 times, for example, vacuum drying at 60-80 ℃ for 8-18 hours, and then calcining in air atmosphere to obtain cerium-zirconium oxide Ce x Zr y O 2 。
(2) Dispersing palladium salt solution into palladium salt dispersion liquid by using water, adding cerium-zirconium oxide into the palladium salt dispersion liquid, stirring, adding a reducing agent for reduction, centrifugally washing, and vacuum drying to obtain the cerium-zirconium oxide supported palladium composite material.
(3) And adding the cerium-zirconium oxide supported palladium composite material into the gold salt solution, stirring for 0.5-2 h, adding urea, heating at 80-100 ℃ for 6-10 h, aging at 15-35 ℃ for 10-15 h, and centrifugally washing and drying to obtain the cerium-zirconium oxide supported palladium-gold composite material.
(4) Placing the cerium-zirconium oxide supported palladium-gold composite material into an etching solution for etching, and after etching, centrifugally washing and drying to obtain the cerium-zirconium oxide supported palladium-gold catalyst; the etching solution is formed by mixing a sodium cyanide aqueous solution with the mass fraction of 2% and a sodium hydroxide aqueous solution with the concentration of 0.1mol/L, wherein the sodium hydroxide aqueous solution is used for adjusting the pH of the etching solution to 11-13. The conditions of centrifugal washing and drying are not particularly limited, and can be selected by a person skilled in the art according to the requirements, and the drying is, for example, 8-18 hours at 40-80 ℃.
The present invention provides in a second aspect a cerium zirconium oxide supported palladium gold catalyst prepared by the preparation method of the present invention described in the first aspect.
The invention provides in a third aspect the use of a cerium zirconium oxide supported palladium gold catalyst prepared by the preparation method of the invention in the first aspect in hydrogen production from formic acid.
In the invention, when the cerium-zirconium oxide supported palladium-gold catalyst is adopted to carry out formic acid hydrogen production, the cerium-zirconium oxide supported palladium-gold catalyst and hydrogen production stock solution are uniformly mixed to carry out hydrogen production reaction; specifically, deionized water is used for carrying out ultrasonic treatment on a cerium-zirconium oxide supported palladium-gold catalyst for 5-15 min, and then the cerium-zirconium oxide supported palladium-gold catalyst is added into hydrogen production stock solution to be uniformly mixed for hydrogen production reaction; in the invention, for example, the hydrogen production stock solution contains formic acid and/or sodium formate, the hydrogen production stock solution takes water as a solvent, the concentration of the formic acid in the hydrogen production stock solution is 1-3 mol/L, and/or the concentration of the sodium formate in the hydrogen production stock solution is 3-7 mol/L, and the consumption of the cerium-zirconium oxide supported palladium-gold catalyst is as follows: adding 0.01-0.03 g of cerium-zirconium oxide supported palladium-gold catalyst into each 20mL of hydrogen production stock solution; the temperature of the hydrogen production reaction is 40-80 ℃.
The invention will be further illustrated by way of example, but the scope of the invention is not limited to these examples. The present invention is capable of other and further embodiments and its several details are capable of modification and variation in accordance with the present invention, as will be apparent to those skilled in the art, without departing from the spirit and scope of the invention as defined in the appended claims.
Example 1
(1) Uniformly mixing cerium nitrate hexahydrate and zirconyl nitrate hydrate by using 25mL of deionized water to obtain a mixed solution, dissolving 15g of sodium hydroxide in 35mL of deionized water to obtain a sodium hydroxide aqueous solution, wherein the molar ratio of the cerium nitrate hexahydrate to the zirconyl nitrate hydrate is 3:1, and the mixed solution contains the cerium nitrate hexahydrate and the zirconyl nitrate hydrate, wherein the sum of the mass percentages of the cerium nitrate hexahydrate and the zirconyl nitrate hydrate is 30%; then adding the sodium hydroxide aqueous solution into the mixed solution, stirring for 30min at the room temperature of 25 ℃ and the rotating speed of 400r/min to obtain emulsion, then transferring the emulsion into a hydrothermal reaction kettle, performing hydrothermal reaction for 24h at the rotating speed of 180 ℃ and the rotating speed of 400r/min, after the reaction is finished, performing centrifugal washing and drying to obtain oxide, and calcining the oxide in the air atmosphere at the temperature of 500 ℃ for 5h to obtain cerium-zirconium oxide.
(2) Dispersing 0.6mL of a chloropalladite solution (palladium salt solution) containing 0.1mol/L of palladium dichloride with 40mL of deionized water to obtain a chloropalladite dispersion (palladium salt dispersion), wherein the pH of the chloropalladite solution is 1; then adding 2g of cerium zirconium oxide into the chloropalladac acid dispersion liquid, stirring for 12 hours at the room temperature of 25 ℃ and the rotating speed of 400r/min, adding 13.78mg of sodium borohydride, reducing for 0.5 hour at the room temperature of 25 ℃ and the rotating speed of 400r/min, and centrifugally washing and drying to obtain the cerium zirconium oxide supported palladium composite material.
(3) Preparing chloroauric acid into a chloroauric acid solution with the concentration of 0.000032mol/L by using 100mL of deionized water; then adding the cerium-zirconium oxide supported palladium composite material obtained in the step (2) into chloroauric acid solution, stirring for 1h at the room temperature of 25 ℃ and the rotating speed of 400r/min, adding 24mg of urea, heating for 8h at the temperature of 90 ℃ and the rotating speed of 400r/min, aging and standing for 12h at the temperature of 25 ℃, and centrifugally washing and drying to obtain the cerium-zirconium oxide supported palladium-gold composite material.
(4) Placing the cerium-zirconium oxide supported palladium-gold composite material in 100mL of etching solution, etching for 10min at the room temperature of 25 ℃, and after etching, centrifugally washing and drying to obtain the cerium-zirconium oxide supported palladium-gold catalyst; the preparation of the etching solution comprises the following steps: adding sodium hydroxide aqueous solution with the concentration of 0.1mol/L into sodium cyanide aqueous solution with the mass fraction of 2%, and regulating the pH value of the sodium cyanide aqueous solution to be 12 to obtain the etching solution.
Example 2
(1) Uniformly mixing cerium nitrate hexahydrate and zirconyl nitrate hydrate by using 25mL of deionized water to obtain a mixed solution, dissolving 15g of sodium hydroxide in 35mL of deionized water to obtain a sodium hydroxide aqueous solution, wherein the molar ratio of the cerium nitrate hexahydrate to the zirconyl nitrate hydrate is 1:3, and the mixed solution contains the cerium nitrate hexahydrate and the zirconyl nitrate hydrate, and the sum of the mass percentages of the cerium nitrate hexahydrate and the zirconyl nitrate hydrate is 30%; then adding the sodium hydroxide aqueous solution into the mixed solution, stirring for 30min at the room temperature of 25 ℃ and the rotating speed of 400r/min to obtain emulsion, then transferring the emulsion into a hydrothermal reaction kettle, performing hydrothermal reaction for 24h at the rotating speed of 180 ℃ and the rotating speed of 400r/min, after the reaction is finished, performing centrifugal washing and drying to obtain oxide, and calcining the oxide in the air atmosphere at the temperature of 500 ℃ for 5h to obtain cerium-zirconium oxide.
(2) Dispersing 0.32mL of a chloropalladite solution (palladium salt solution) containing 0.1mol/L of palladium dichloride with 40mL of deionized water to obtain a chloropalladite dispersion (palladium salt dispersion), wherein the pH of the chloropalladite solution is 1; then adding 1.07g of cerium zirconium oxide into the chloropalladac acid dispersion liquid, stirring for 12 hours at the room temperature of 25 ℃ and the rotating speed of 400r/min, adding 7.35mg of sodium borohydride, reducing for 0.5 hour at the room temperature of 25 ℃ and the rotating speed of 400r/min, and centrifugally washing and drying to obtain the cerium zirconium oxide supported palladium composite material.
(3) The procedure is as in step (3) of example 1.
(4) The procedure is as in step (4) of example 1.
Example 3
(1) Uniformly mixing cerium nitrate hexahydrate and zirconyl nitrate hydrate by using 25mL of deionized water to obtain a mixed solution, dissolving 15g of sodium hydroxide in 35mL of deionized water to obtain a sodium hydroxide aqueous solution, wherein the molar ratio of the cerium nitrate hexahydrate to the zirconyl nitrate hydrate is 1:1, and the mixed solution contains 30 percent of the sum of the mass percentages of the cerium nitrate hexahydrate and the zirconyl nitrate hydrate; then adding the sodium hydroxide aqueous solution into the mixed solution, stirring for 30min at the room temperature of 25 ℃ and the rotating speed of 400r/min to obtain emulsion, then transferring the emulsion into a hydrothermal reaction kettle, performing hydrothermal reaction for 24h at the rotating speed of 180 ℃ and the rotating speed of 400r/min, after the reaction is finished, performing centrifugal washing and drying to obtain oxide, and calcining the oxide in the air atmosphere at the temperature of 500 ℃ for 5h to obtain cerium-zirconium oxide.
(2) Dispersing 1.12mL of a chloropalladite solution (palladium salt solution) containing 0.1mol/L of palladium dichloride with 40mL of deionized water to obtain a chloropalladite dispersion (palladium salt dispersion), wherein the pH of the chloropalladite solution is 1; then adding 3.733g of cerium zirconium oxide into the chloropalladac acid dispersion liquid, stirring for 12 hours at the room temperature of 25 ℃ and the rotating speed of 400r/min, adding 25.72mg of sodium borohydride, reducing for 0.5 hour at the room temperature of 25 ℃ and the rotating speed of 400r/min, and centrifugally washing and drying to obtain the cerium zirconium oxide supported palladium composite material.
(3) The procedure is as in step (3) of example 1.
(4) The procedure is as in step (4) of example 1.
Example 4
Example 4 is substantially the same as example 1 except that:
the step (1) is as follows: uniformly mixing cerium nitrate hexahydrate and zirconyl nitrate hydrate by using 25mL of deionized water to obtain a mixed solution, dissolving 15g of sodium hydroxide in 35mL of deionized water to obtain a sodium hydroxide aqueous solution, wherein the molar ratio of the cerium nitrate hexahydrate to the zirconyl nitrate hydrate is 0.5:3, and the mixed solution contains 30% of the sum of the mass percentages of the cerium nitrate hexahydrate and the zirconyl nitrate hydrate; then adding the sodium hydroxide aqueous solution into the mixed solution, stirring for 30min at the room temperature of 25 ℃ and the rotating speed of 400r/min to obtain emulsion, then transferring the emulsion into a hydrothermal reaction kettle, performing hydrothermal reaction for 24h at the rotating speed of 180 ℃ and the rotating speed of 400r/min, after the reaction is finished, performing centrifugal washing and drying to obtain oxide, and calcining the oxide in the air atmosphere at the temperature of 500 ℃ for 5h to obtain cerium-zirconium oxide.
Example 5
Example 5 is substantially the same as example 1 except that:
the step (1) is as follows: uniformly mixing cerium nitrate hexahydrate and zirconyl nitrate hydrate by using 25mL of deionized water to obtain a mixed solution, dissolving 15g of sodium hydroxide in 35mL of deionized water to obtain a sodium hydroxide aqueous solution, wherein the molar ratio of the cerium nitrate hexahydrate to the zirconyl nitrate hydrate is 3:0.5, and the mixed solution contains 30% of the sum of the mass percentages of the cerium nitrate hexahydrate and the zirconyl nitrate hydrate; then adding the sodium hydroxide aqueous solution into the mixed solution, stirring for 30min at the room temperature of 25 ℃ and the rotating speed of 400r/min to obtain emulsion, then transferring the emulsion into a hydrothermal reaction kettle, performing hydrothermal reaction for 24h at the rotating speed of 180 ℃ and the rotating speed of 400r/min, after the reaction is finished, performing centrifugal washing and drying to obtain oxide, and calcining the oxide in the air atmosphere at the temperature of 500 ℃ for 5h to obtain cerium-zirconium oxide.
Example 6
Example 6 is substantially the same as example 1 except that:
the step (2) is as follows: dispersing 0.16mL of a chloropalladite solution (palladium salt solution) containing 0.1mol/L of palladium dichloride with 40mL of deionized water to obtain a chloropalladite dispersion (palladium salt dispersion), wherein the pH of the chloropalladite solution is 1; then adding 0.53g of cerium zirconium oxide into the chloropalladac acid dispersion liquid, stirring for 12 hours at the room temperature of 25 ℃ and the rotating speed of 400r/min, adding 3.675mg of sodium borohydride, reducing for 0.5 hour at the room temperature of 25 ℃ and the rotating speed of 400r/min, and centrifugally washing and drying to obtain the cerium zirconium oxide supported palladium composite material.
Example 7
Example 7 is substantially the same as example 1 except that:
the step (2) is as follows: dispersing 1.28mL of a chloropalladite solution (palladium acid solution) containing 0.1mol/L of palladium dichloride with 40mL of deionized water to obtain a chloropalladite dispersion (palladium acid dispersion), wherein the pH of the chloropalladite solution is 1; then adding 4.27g of cerium zirconium oxide into the chloropalladac acid dispersion liquid, stirring for 12 hours at the room temperature of 25 ℃ and the rotating speed of 400r/min, adding 29.4mg of sodium borohydride, reducing for 0.5 hour at the room temperature of 25 ℃ and the rotating speed of 400r/min, and centrifugally washing and drying to obtain the cerium zirconium oxide supported palladium composite material.
Comparative example 1
(1) Uniformly mixing cerium dioxide powder and zirconium dioxide powder to obtain composite powder; in the composite powder, the molar ratio of the cerium oxide powder to the zirconium dioxide powder is 3:1.
(2) Dispersing 0.6mL of a chloropalladite solution (palladium salt solution) containing 0.1mol/L of palladium dichloride with 40mL of deionized water to obtain a chloropalladite dispersion (palladium salt dispersion), wherein the pH of the chloropalladite solution is 1; then adding 2g of composite powder into the chloropalladac acid dispersion liquid, stirring for 12 hours at the room temperature of 25 ℃ and the rotating speed of 400r/min, adding 13.78mg of sodium borohydride, reducing for 0.5 hour at the room temperature of 25 ℃ and the rotating speed of 400r/min, and centrifugally washing and drying to obtain the oxide-loaded palladium composite material.
(3) Preparing chloroauric acid into a chloroauric acid solution with the concentration of 0.000032mol/L by using 100mL of deionized water; then adding the oxide load palladium composite material obtained in the step (2) into chloroauric acid solution, stirring for 1h at the room temperature of 25 ℃ and the rotating speed of 400r/min, then adding 24mg of urea, heating for 8h at the temperature of 90 ℃ and the rotating speed of 400r/min, aging and standing for 12h at the temperature of 25 ℃, and centrifugally washing and drying to obtain the oxide load palladium-gold composite material.
(4) Placing the oxide supported palladium-gold composite material in 100mL of etching solution, etching for 10min at the room temperature of 25 ℃, and after etching, centrifugally washing and drying to obtain the oxide supported palladium-gold catalyst; the preparation of the etching solution comprises the following steps: adding sodium hydroxide aqueous solution with the concentration of 0.1mol/L into sodium cyanide aqueous solution with the mass fraction of 2%, and regulating the pH value of the sodium cyanide aqueous solution to be 12 to obtain the etching solution.
Comparative example 2
(1) Uniformly mixing cerium nitrate hexahydrate and zirconyl nitrate hydrate by using 25mL of deionized water to obtain a mixed solution, dissolving 15g of sodium hydroxide in 35mL of deionized water to obtain a sodium hydroxide aqueous solution, wherein the molar ratio of the cerium nitrate hexahydrate to the zirconyl nitrate hydrate is 3:1, and the mixed solution contains the cerium nitrate hexahydrate and the zirconyl nitrate hydrate, wherein the sum of the mass percentages of the cerium nitrate hexahydrate and the zirconyl nitrate hydrate is 30%; then adding the sodium hydroxide aqueous solution into the mixed solution, stirring for 30min at the room temperature of 25 ℃ and the rotating speed of 400r/min to obtain emulsion, then transferring the emulsion into a hydrothermal reaction kettle, performing hydrothermal reaction for 24h at the rotating speed of 180 ℃ and the rotating speed of 400r/min, after the reaction is finished, performing centrifugal washing and drying to obtain oxide, and calcining the oxide in the air atmosphere at the temperature of 500 ℃ for 5h to obtain cerium-zirconium oxide.
(2) Dispersing 0.632mL of a chloropalladite solution (palladium salt solution) containing 0.1mol/L of palladium dichloride with 40mL of deionized water to obtain a chloropalladite dispersion (palladium salt dispersion), wherein the pH of the chloropalladite solution is 1; then adding 2g of cerium zirconium oxide into the chloropalladac acid dispersion liquid, stirring for 12 hours at the room temperature of 25 ℃ at the rotating speed of 400r/min, adding 13.78mg of sodium borohydride, reducing for 0.5 hour at the room temperature of 25 ℃ at the rotating speed of 400r/min, and centrifugally washing and drying to obtain the cerium zirconium oxide supported palladium catalyst.
Comparative example 3
(1) Uniformly mixing cerium nitrate hexahydrate and zirconyl nitrate hydrate by using 25mL of deionized water to obtain a mixed solution, dissolving 15g of sodium hydroxide in 35mL of deionized water to obtain a sodium hydroxide aqueous solution, wherein the molar ratio of the cerium nitrate hexahydrate to the zirconyl nitrate hydrate is 3:1, and the mixed solution contains the cerium nitrate hexahydrate and the zirconyl nitrate hydrate, wherein the sum of the mass percentages of the cerium nitrate hexahydrate and the zirconyl nitrate hydrate is 30%; then adding the sodium hydroxide aqueous solution into the mixed solution, stirring for 30min at the room temperature of 25 ℃ and the rotating speed of 400r/min to obtain emulsion, then transferring the emulsion into a hydrothermal reaction kettle, performing hydrothermal reaction for 24h at the rotating speed of 180 ℃ and the rotating speed of 400r/min, after the reaction is finished, performing centrifugal washing and drying to obtain oxide, and calcining the oxide in the air atmosphere at the temperature of 500 ℃ for 5h to obtain cerium-zirconium oxide.
(2) Dispersing 0.6mL of a chloropalladite solution (palladium salt solution) containing 0.1mol/L of palladium dichloride with 40mL of deionized water to obtain a chloropalladite dispersion (palladium salt dispersion), wherein the pH of the chloropalladite solution is 1; then adding 2g of cerium zirconium oxide into the chloropalladac acid dispersion liquid, stirring for 12 hours at the room temperature of 25 ℃ and the rotating speed of 400r/min, adding 13.78mg of sodium borohydride, reducing for 0.5 hour at the room temperature of 25 ℃ and the rotating speed of 400r/min, and centrifugally washing and drying to obtain the cerium zirconium oxide supported palladium composite material.
(3) Preparing chloroauric acid into a chloroauric acid solution with the concentration of 0.000032mol/L by using 100mL of deionized water; then adding the cerium-zirconium oxide supported palladium composite material obtained in the step (2) into chloroauric acid solution, stirring for 1h at the room temperature of 25 ℃ and the rotating speed of 400r/min, adding 24mg of urea, heating for 8h at the temperature of 90 ℃ and the rotating speed of 400r/min, aging and standing for 12h at the temperature of 25 ℃, and centrifugally washing and drying to obtain the cerium-zirconium oxide supported palladium-gold catalyst.
In the above examples and comparative examples, if the amount of cerium-zirconium oxide is relatively large, the respective corresponding steps (1) may be repeated a plurality of times until the desired amount of cerium-zirconium oxide is obtained and the subsequent steps are performed.
The invention tests the catalytic effect of the hydrogen production reaction of formic acid on the catalysts finally prepared in each example and each comparative example, and the hydrogen production test method of formic acid comprises the following steps:
preparing a mixed solution of formic acid and sodium formate by using water as a solvent, wherein 200mL of a hydrogen production stock solution contains 1mol/L formic acid, and 3mol/L sodium formate; ultrasonic dispersing 0.1g of catalyst with 5mL of deionized water for 10min to obtain catalyst dispersion; then adding a catalyst dispersion liquid into 200mL of the hydrogen production stock solution to carry out hydrogen production reaction; after hydrogen production reaction is carried out at 80 ℃ for 10min, a conversion frequency value (TOF value) is obtained, the result is shown in table 1, and the result of measuring the content of CO in the gas product in the first 10min is shown in table 1, wherein the content of CO in the gas product is detected by a gas chromatograph equipped with a hydrogen flame detector.
TABLE 1
The catalyst prepared in each example and each comparative example is also used for 3-cycle catalytic formic acid hydrogen production, after each reaction for 10min according to the formic acid hydrogen production test method of the invention, the catalyst is centrifuged and washed with water, and the formic acid hydrogen production test is repeatedly carried out for 3 times, so that the 3 rd cycle conversion frequency value (TOF value) result is obtained, and the first formic acid hydrogen production test is recorded as the 1 st cycle in Table 2 as shown in Table 2.
TABLE 2
As can be seen from the data in tables 1 and 2, the cerium-zirconium oxide supported palladium-gold catalyst prepared by the invention has the advantages of high catalytic efficiency, good catalytic stability and effective carbon monoxide poisoning resistance in hydrogen production by formic acid; the conversion frequency value (TOF value) of the cerium-zirconium oxide supported palladium-gold catalyst prepared in some preferred embodiments of the invention can reach 4500h -1 Above, carbon monoxide poisoning resistanceThe capability is strong, the carbon monoxide content in the gas product is not higher than 20ppm and even can be lower than 5ppm, the catalytic stability of the cerium-zirconium oxide supported palladium-gold catalyst is good, and after 3 times of circulating catalytic formic acid hydrogen production, the TOF value retention rate can still reach more than 58% and even can reach as high as 81.1%, so that the catalyst has quite high catalytic stability for the formic acid hydrogen production catalyst.
The invention is not described in detail in a manner known to those skilled in the art.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will 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 and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a cerium-zirconium oxide supported palladium-gold catalyst, which is characterized by comprising the following steps:
(1) Uniformly mixing cerium nitrate hexahydrate and zirconium oxynitrate hydrate with water to obtain a mixed solution, adding sodium hydroxide solution into the mixed solution for hydrothermal reaction to obtain an oxide, and calcining the oxide to obtain cerium zirconium oxide;
(2) Dispersing a palladium salt solution into a palladium salt dispersion liquid by using water, adding cerium-zirconium oxide into the palladium salt dispersion liquid, stirring, and adding a reducing agent for reduction to obtain a cerium-zirconium oxide supported palladium composite material;
(3) Adding a cerium-zirconium oxide supported palladium composite material and urea into the gold salt solution to react to obtain the cerium-zirconium oxide supported palladium-gold composite material; the gold salt solution is chloroauric acid aqueous solution; the reaction is that heating treatment is carried out at 80-100 ℃ for 6-10 hours, and then aging is carried out at 15-35 ℃ for 10-15 hours;
(4) And placing the cerium-zirconium oxide supported palladium-gold composite material into an etching solution for etching to prepare the cerium-zirconium oxide supported palladium-gold catalyst.
2. The method of claim 1, wherein in step (1):
the molar ratio of the cerium nitrate hexahydrate to the amount of the zirconyl nitrate hydrate is (1-3): (1-3);
the mixed solution contains 20-40% of cerium nitrate hexahydrate and zirconyl nitrate hydrate by mass percent;
the concentration of the sodium hydroxide solution is 8-12 mol/L;
the volume ratio of the mixed solution to the sodium hydroxide solution is 1: (1-2);
the temperature of the hydrothermal reaction is 150-200 ℃, and the time of the hydrothermal reaction is 12-24 hours;
the calcination is performed in an air atmosphere; and/or
The calcination temperature is 400-800 ℃, and the calcination time is 4-8 hours.
3. The method of claim 1, wherein in step (2):
the palladium salt solution is a palladium chloride acid solution, the palladium chloride acid solution is prepared from hydrochloric acid with the pH value of 0-2 and palladium dichloride, and the concentration of the palladium dichloride in the palladium chloride acid solution is 0.05-0.15 mol/L; and/or
The volume ratio of the water to the palladium salt solution is (50-80): 1.
4. the method of claim 1, wherein in step (2):
the mass ratio of the cerium zirconium oxide to the reducing agent is (130-150): 1, a step of;
the molar ratio of palladium contained in the palladium salt solution to the reducing agent is 1: (3-12);
the reducing agent is one or more of sodium borohydride, potassium borohydride and hydrazine hydrate;
the stirring time is 6-15 h, and the stirring rotating speed is 300-800 r/min; and/or
The reduction time is 0.5-2 h.
5. The method of claim 1, wherein in step (3):
the concentration of the chloroauric acid aqueous solution is 0.00002-0.00004 mol/L.
6. The method of manufacturing according to claim 1, characterized in that:
the molar ratio of palladium contained in the palladium salt solution to gold contained in the gold salt solution is (10-35): 1, a step of; and/or
The molar ratio of gold contained in the gold salt solution to the urea is 1: (110-140).
7. The method of claim 1, wherein in step (4):
the etching solution is an etchant aqueous solution with pH of 11-13;
the etchant contained in the etchant aqueous solution is sodium cyanide and/or sodium cyanate;
the etchant aqueous solution contains 1-3% of etchant by mass.
8. The method of claim 1, wherein in step (4):
the etching temperature is 15-35 ℃, and the etching time is 5-120 min.
9. A cerium zirconium oxide supported palladium gold catalyst produced by the production method of any one of claims 1 to 8.
10. Use of a cerium-zirconium oxide supported palladium-gold catalyst prepared by the preparation method of any one of claims 1 to 8 in hydrogen production from formic acid.
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