CN110404535B - Supported palladium catalyst, preparation method and application - Google Patents
Supported palladium catalyst, preparation method and application Download PDFInfo
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- CN110404535B CN110404535B CN201910726853.6A CN201910726853A CN110404535B CN 110404535 B CN110404535 B CN 110404535B CN 201910726853 A CN201910726853 A CN 201910726853A CN 110404535 B CN110404535 B CN 110404535B
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 41
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 230000009467 reduction Effects 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 4
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 4
- 229960005055 sodium ascorbate Drugs 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 238000000935 solvent evaporation Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 9
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000002086 nanomaterial Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000725 suspension Substances 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- -1 palladium ions Chemical class 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6482—Vanadium
-
- B01J35/61—
-
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- 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
- C01B2203/1064—Platinum group metal catalysts
-
- 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
- C01B2203/1082—Composition of support materials
-
- 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The disclosure provides a supported palladium catalyst, a preparation method and application thereof. The preparation method comprises the following steps: adding a reducing agent into the dispersion liquid of the cerium dioxide for reduction treatment, mixing the cerium dioxide after reduction treatment with palladium chloride, and heating in an ammonia atmosphere to enable palladium to grow on the surface of the cerium dioxide in situ to obtain the supported palladium catalyst of the cerium dioxide supported palladium nanoparticles. The preparation method disclosed by the invention has the advantages that the adsorption efficiency and stability of the treated cerium dioxide on Pd ions are obviously improved, and CeO 2 The catalytic activity and the cycling stability of @ Pd are also obviously improved. The supported palladium catalyst prepared by the method can greatly improve the hydrogen production rate of formaldehyde hydrogen production.
Description
Technical Field
The disclosure relates to the technical field of catalytic hydrogen production, and particularly relates to a supported palladium catalyst, and a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The green clean energy comprises solar energy, wind energy, water energy, hydrogen energy and the like, wherein the hydrogen energy is considered as the main energy of human beings in the future due to the advantages of abundant reserves, high calorific value, convenience in storage and transportation, various utilization forms, environmental friendliness, no toxicity, no pollution and the like. The existing methods for preparing hydrogen mainly comprise hydrocarbon reforming hydrogen production, water electrolysis hydrogen production, biological hydrogen production and chemical hydride catalytic hydrogen production. In the eighties of the eighteenth century, it is reported that formaldehyde in an aqueous solution containing high-concentration alkali can quantitatively generate hydrogen at room temperature to catalyze formaldehyde to prepare hydrogen, and the mechanism of the method is generally thought to be that formaldehyde and water molecules respectively provide one hydrogen atom, that is, 1mol of formaldehyde molecules can generate 1mol of hydrogen.
Palladium (Pd) is a silvery white transition metal, has good ductility and plasticity, and can be forged, rolled and drawn. The bulk metal palladium can absorb a large amount of hydrogen, so that the volume is remarkably expanded, becomes brittle and even breaks into fragments. Palladium is an indispensable key material in the high-tech fields of aerospace, aviation, navigation, weapons, nuclear energy and the like and in the automobile manufacturing industry, and is also an investment variety which is not neglected in the international precious metal investment market; can be used for manufacturing dental materials, watches, surgical instruments and the like, and is mainly used as a catalyst in chemistry. However, the noble metal Pd has the defects of high cost, easy agglomeration and inactivation and the like.
Disclosure of Invention
In order to solve the defects of the prior art, the purpose of the present disclosure is to provide a supported palladium catalyst, a preparation method and an application thereof, and the hydrogen production rate of hydrogen production from formaldehyde can be greatly increased by using the supported palladium catalyst.
In order to achieve the purpose, the technical scheme of the disclosure is as follows:
in a first aspect, the present disclosure provides a preparation method of a supported palladium catalyst, including adding a reducing agent into a cerium dioxide dispersion liquid for reduction treatment, mixing the reduced cerium dioxide with palladium chloride, and heating in an ammonia atmosphere to allow palladium to grow in situ on the surface of the cerium dioxide to obtain the supported palladium catalyst of cerium dioxide supported palladium nanoparticles.
The preparation method provided by the disclosure is based on the huge specific surface area of the nano particles, so that the surface of cerium dioxide has strong reducing capability, and palladium ions are carried out on a solid containing the palladium ions through NH 3 After complexing, in a high-temperature environment, palladium ions can be uniformly adsorbed on the surface of cerium dioxide, and finally palladium nanoparticles are attached to the surface of the cerium dioxide in situ to form ideal CeO 2 @ Pd nano catalyst.
Experiments in the disclosure show that the supported palladium catalyst of cerium dioxide supported palladium nanoparticles prepared by the method has a high hydrogen production rate. The catalyst prepared by using vanadium pentoxide as a carrier has a low hydrogen production rate.
In a second aspect, the present disclosure provides a supported palladium catalyst obtained by the above preparation method.
In a third aspect, the disclosure provides an application of the supported palladium catalyst in hydrogen production from formaldehyde.
In a fourth aspect, the present disclosure provides a method for producing hydrogen from formaldehyde, in which the supported palladium catalyst is added to a solution containing formaldehyde, and the reaction is performed at room temperature.
The beneficial effect of this disclosure does:
(1) the preparation method disclosed by the invention adopts a liquid-phase reduction mode to pretreat the cerium dioxide, the adsorption efficiency and stability of the treated cerium dioxide on Pd ions are obviously improved, and CeO 2 The catalytic activity and the cycling stability of @ Pd are also obviously improved.
(2) The supported palladium catalyst of the cerium dioxide supported palladium nanoparticles prepared by the method can obviously improve the catalytic activity of hydrogen production from formaldehyde.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure and are not to limit the disclosure.
FIG. 1 shows CeO prepared in example 1 of the present disclosure 2 X-ray diffraction pattern of @ Pd supported catalyst;
FIG. 2 shows CeO prepared in example 1 of the present disclosure 2 Transmission electron micrograph of @ Pd supported catalyst;
FIG. 3 is V prepared according to example 2 of the present disclosure 2 O 5 X-ray diffraction pattern of @ Pd supported catalyst;
FIG. 4 is V prepared according to example 2 of the present disclosure 2 O 5 Transmission electron micrograph of @ Pd supported catalyst;
FIG. 5 shows CeO prepared in example 1 of the present disclosure 2 @ Pd Supported catalyst and V prepared in example 2 2 O 5 The comparison curve of the results of the @ Pd supported catalyst for catalyzing the formaldehyde to produce hydrogen;
FIG. 6 shows CeO prepared in example 3 of the present disclosure 2 @ Pd supported catalyst cycle life test curve.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the defects of high cost, easy agglomeration and inactivation and the like of the existing noble metal Pd, the disclosure provides a supported palladium catalyst, and a preparation method and application thereof.
In a typical embodiment of the present disclosure, a reducing agent is added to a cerium dioxide dispersion to perform a reduction treatment, and then the reduced cerium dioxide and palladium chloride are mixed and heated in an ammonia atmosphere to in-situ grow palladium on the surface of the cerium dioxide to obtain a supported palladium catalyst of cerium dioxide supported palladium nanoparticles.
The preparation method provided by the disclosure is based on the huge specific surface area of the nano particles, so that the surface of cerium dioxide has strong reducing capability, and palladium ions are carried out on a solid containing the palladium ions through NH 3 After complexing, in a high-temperature environment, palladium ions can be uniformly adsorbed on the surface of cerium dioxide, and finally palladium nanoparticles are attached to the surface of the cerium dioxide in situ to form ideal CeO 2 @ Pd nano catalyst.
Experiments in the disclosure find that the supported palladium catalyst of the cerium dioxide supported palladium nanoparticles prepared by the method has a high hydrogen production rate. The catalyst prepared by using vanadium pentoxide as a carrier has a low hydrogen production rate.
The principle of the disclosure is as follows: the surface of the ceria is reduced after the addition of the reducing agent, and then [ Pd (NH) is adsorbed 3 ) 2 ] 2+ And then after adsorption [ Pd (NH) ] 3 ) 2 ] 2+ The reduced ceria is oxidized such that palladium grows in situ on the ceria surface. The reaction formula is as follows:
Pd 2+ +2NH 3 →[Pd(NH 3 ) 2 ] 2+
Ce x O y +[Pd(NH 3 ) 2 ] 2+ →CeO 2 @Pd+NH 3
in one or more embodiments of this embodiment, the reduction treatment is performed by sonication. The ultrasonic treatment time is 1-20 min.
In one or more embodiments of this embodiment, the reducing agent is NaBH 4 Sodium citrate or sodium ascorbate.
In one or more embodiments of this embodiment, the solid separated after treatment with the reducing agent is reduced ceria.
In this series of examples, the method of separation is centrifugation, filtration, sedimentation or solvent evaporation.
In one or more embodiments of this embodiment, the concentration of the reducing agent in the reduction treatment is 5 to 15 mg/mL.
In one or more embodiments of this embodiment, the heating temperature is 200 to 500 ℃.
In one or more embodiments of this embodiment, the ceria is obtained by hydrothermal synthesis. For example: mai H X, Sun L D, Zhang Y W, et al, shape-Selective Synthesis and Oxygen Storage Beihavior of Ceria Nanopoldra, Nanorods, and Nanocubes the Journal of Physical Chemistry B,2005,109(51) 24380-.
In another embodiment of the present disclosure, there is provided a supported palladium catalyst obtained by the above preparation method.
In a third embodiment of the present disclosure, an application of the above supported palladium catalyst in hydrogen production from formaldehyde is provided.
In a fourth embodiment of the present disclosure, a method for producing hydrogen from formaldehyde is provided, in which the supported palladium catalyst is added to a solution containing formaldehyde, and the reaction is performed at room temperature.
The room temperature in the present disclosure refers to the indoor ambient temperature, and is generally 15 to 30 ℃.
In one or more embodiments of the present disclosure, the concentration of formaldehyde in the solution is 0.5 to 0.6 mol/L.
In one or more embodiments of this embodiment, the solution comprises sodium hydroxide.
In the series of embodiments, the concentration of the sodium hydroxide is 0.9-1.1 mol/L.
In order to make the technical solutions of the present disclosure more clearly understood by those skilled in the art, the technical solutions of the present disclosure will be described in detail below with reference to specific embodiments.
Example 1:
(1) mixing the nanometer material CeO 2 Dispersed in 8mL ethanol to prepare 10mg/mL CeO 2 Suspending liquid, and performing ultrasonic treatment for 60min to ensure that CeO is dissolved 2 And (4) uniformly dispersing.
(2) 1mL of NaBH was added to the suspension obtained in step (1) 4 (5mg/mL) for CeO 2 And carrying out reduction treatment, and carrying out ultrasonic reduction for 10 min.
(3) Reducing the CeO 2 The supernatant was removed by centrifugation and the pellet was dried in a vacuum oven for 5 h.
(4) 10mg of palladium dichloride solid was mixed with the CeO obtained in step (2) 2 The reduced powder (30mg) was placed in a tube furnace in N 2 The temperature was programmed to 300 ℃ in the atmosphere.
(5) Introducing NH into the tube furnace in the step (4) 3 Reacting for 10 hours to obtain CeO 2 HRTEM dispersed in ethanol as shown in FIG. 2, the @ Pd supported catalyst was supportedXRD analysis of the type catalyst As shown in FIG. 1, the supported catalyst was supported with Pd in an amount of 4.55 wt% by ICP.
(6) Mixing the nano CeO 2 、CeO 2 @ Pd 15mg of each catalyst was weighed as formaldehyde for hydrogen production at room temperature, and dispersed in 100mL of a mixed solution of HCHO and NaOH (C) HCHO ＝0.567mol/L，C NaOH ＝1mol/L)。
(7) The mixture was stirred vigorously at a temperature of 30 ℃.
(8) The test was performed every 5min by using a gas chromatograph, and the test results are shown in FIG. 5, which indicates that CeO was present 2 Catalytic activity ratio of @ Pd heterojunction to pure CeO 2 More strongly, CeO 2 The average hydrogen production rate of the @ Pd catalyzed formaldehyde hydrogen production is 2.133 mL/min.
The nano material in the step (1) is CeO prepared by a hydrothermal synthesis method 2 A metal oxide.
Example 2:
(1) mixing the nano material V 2 O 5 Dispersing in 8mL ethanol to prepare 8mg/mL V 2 O 5 Suspending liquid, and performing ultrasonic treatment for 30min to obtain V 2 O 5 And (4) uniformly dispersing.
(2) Adding 1mL of NaBH into the suspension obtained in the step (1) 4 (7mg/mL) for V 2 O 5 And (4) carrying out reduction treatment, and carrying out ultrasonic reduction for 20 min.
(3) Reducing the V 2 O 5 The supernatant was removed by centrifugation and the precipitate was dried in a vacuum oven for 5 h.
(4) Reacting 10mg of palladium dichloride solid with V obtained in step (2) 2 O 5 The reduced powder (30mg) was placed in a tube furnace in N 2 The temperature was programmed to 200 ℃ in the atmosphere.
(5) Introducing NH into the tube furnace in the step (4) 3 Reacting for 8h to obtain V 2 O 5 The TEM of the @ Pd supported catalyst dispersed in ethanol is shown in FIG. 4, and the XRD analysis of the nanomaterial is shown in FIG. 3.
(6) Will nano V 2 O 5 、V 2 O 5 @ Pd 15mg of the catalyst was weighed out separately as a catalyst for producing hydrogen from formaldehyde at room temperature, and dispersed in 100mL of the catalystMixed solution of HCHO and NaOH (C) HCHO ＝0.567mol/L，C NaOH ＝1mol/L)。
(7) The mixture was stirred vigorously at a temperature of 30 ℃.
(8) The test was performed every 5min by using a gas chromatograph, and the test results are shown in FIG. 5, which shows that V is 2 O 5 Catalytic activity ratio pure state V of @ Pd heterojunction 2 O 5 More strongly, V 2 O 5 The average rate of the @ Pd catalysis for preparing the hydrogen from the formaldehyde is 0.867mL/min and is close to the CeO 2 @ 1/3 for the Pd hydrogen production rate.
The nano material in the step (1) is V prepared by a hydrothermal synthesis method 2 O 5 A metal oxide.
As can be seen from FIG. 5, CeO in pure form 2 、V 2 O 5 Can not catalyze formaldehyde to prepare hydrogen; CeO (CeO) 2 The @ Pd has the highest efficiency of catalyzing formaldehyde to produce hydrogen, and the average hydrogen production rate is 2.133 mL/min; v 2 O 5 The average rate of the @ Pd catalysis for preparing the hydrogen from the formaldehyde is 0.867mL/min and is less than that of CeO 2 @ Pd hydrogen production rate. Thus, CeO was found 2 The catalytic activity of @ Pd is the best.
Example 3:
(1) mixing the nanometer material CeO 2 Dispersed in 8mL ethanol to prepare 8mg/mL CeO 2 Suspending liquid, and performing ultrasonic treatment for 40min to obtain CeO 2 And (4) uniformly dispersing.
(2) 1mL of sodium ascorbate (5mg/mL) was added to the suspension obtained in step (1) to the CeO solution 2 And (4) carrying out reduction treatment, and carrying out ultrasonic reduction for 20 min.
(3) Reducing the CeO 2 The supernatant was removed by centrifugation and the pellet was dried in a vacuum oven for 5 h.
(4) 10mg of palladium dichloride solid was mixed with the CeO obtained in step (2) 2 The reduced powder (30mg) was placed in a tube furnace in N 2 The temperature was programmed to 400 ℃ in the atmosphere.
(5) Introducing NH into the tube furnace in the step (4) 3 Reacting for 3 hours to obtain CeO 2 @ Pd supported catalyst;
(6) adding CeO 2 @ Pd 15mg of catalyst for hydrogen production by formaldehyde at room temperature is weighed and dispersed in 100mMixed solution of L of HCHO and NaOH (C) HCHO ＝0.567mol/L，C NaOH ＝1mol/L)。
(7) The mixture was stirred vigorously at a temperature of 30 ℃.
(8) The reaction was cycled 5 times every 5min using a gas chromatograph, and the results are shown in FIG. 6. Shows that the efficiency of the formaldehyde hydrogen production is hardly changed after 5 times of circulation, and shows that CeO 2 The @ Pd heterojunction is good in catalytic stability when used for preparing hydrogen from formaldehyde at room temperature.
The nano material in the step (1) is CeO prepared by a hydrothermal synthesis method 2 A metal oxide.
Example 4:
(1) mixing the nano material V 2 O 5 Dispersing in 8mL ethanol to prepare 6mg/mL V 2 O 5 Suspending liquid, and performing ultrasonic treatment for 10min to obtain V 2 O 5 And (4) uniformly dispersing.
(2) To the suspension obtained in step (1), 1mL of sodium ascorbate (15mg/mL) was added to the suspension, for V 2 O 5 And (4) carrying out reduction treatment, and carrying out ultrasonic reduction for 5 min.
(3) Reducing the V 2 O 5 The supernatant was removed by centrifugation and the pellet was dried in a vacuum oven for 5 h.
(4) 5mg of palladium dichloride solid was mixed with V obtained in step (2) 2 O 5 The reduced powder (30mg) was placed in a tube furnace in N 2 The temperature was programmed to 500 ℃ in the atmosphere.
(5) Introducing NH into the tube furnace in the step (4) 3 Reacting for 2h to obtain V 2 O 5 @ Pd supported catalyst.
The nano material in the step (1) is V prepared by a hydrothermal synthesis method 2 O 5 A metal oxide.
Example 5:
(1) mixing the nanometer material CeO 2 Dispersed in 8mL ethanol to prepare 5mg/mL CeO 2 Suspending the solution, and performing ultrasonic treatment for 10min to ensure that CeO 2 And (4) uniformly dispersing.
(2) To the suspension obtained in step (1), 1mL of sodium citrate (15mg/mL) was added to the CeO 2 Carrying out reduction treatment and ultrasonic reduction4min。
(3) Reducing CeO 2 The supernatant was removed by centrifugation and the pellet was dried in a vacuum oven for 5 h.
(4) 2mg of palladium dichloride solid and CeO obtained in the step (2) 2 The reduced powder (30mg) was placed in a tube furnace in N 2 The temperature was programmed to 350 ℃ in the atmosphere.
(5) Introducing NH into the tube furnace in the step (4) 3 Reacting for 4 hours to obtain CeO 2 @ Pd supported catalyst;
the nano material in the step (1) is CeO prepared by a hydrothermal synthesis method 2 A metal oxide.
Example 6:
(1) mixing the nano material V 2 O 5 Dispersing in 8mL ethanol to prepare 3mg/mL V 2 O 5 Suspending liquid, and performing ultrasonic treatment for 7min to obtain V 2 O 5 And (4) uniformly dispersing.
(2) To the suspension obtained in step (1), 1mL of sodium citrate (12mg/mL) was added to the suspension, vs. V 2 O 5 And (4) carrying out reduction treatment, and carrying out ultrasonic reduction for 10 min.
(3) Reducing the V 2 O 5 The supernatant was removed by centrifugation and the pellet was dried in a vacuum oven for 5 h.
(4) Reacting 2mg of palladium dichloride solid with V obtained in step (2) 2 O 5 The reduced powder (30mg) was placed in a tube furnace in N 2 The temperature was programmed to 450 ℃ in the atmosphere.
(5) Introducing NH into the tubular furnace in the step (4) 3 Reacting for 3h to obtain V 2 O 5 @ Pd supported catalyst.
The nano material in the step (1) is V prepared by a hydrothermal synthesis method 2 O 5 A metal oxide.
The above description is only a preferred embodiment of the present disclosure and is not intended to limit the present disclosure, and various modifications and changes may be made to the present disclosure by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.
Claims (10)
1. A preparation method of a supported palladium catalyst is characterized in that a reducing agent is added into a dispersion liquid of nano cerium dioxide for reduction treatment, and then the cerium dioxide after reduction treatment and palladium chloride are mixed and heated in an ammonia atmosphere to enable palladium to grow on the surface of the cerium dioxide in situ to obtain the supported palladium catalyst of cerium dioxide supported palladium nanoparticles;
heating to 300-500 ℃;
the reducing agent is NaBH 4 Sodium citrate or sodium ascorbate;
or the concentration of the reducing agent in the reduction treatment is 5-15 mg/mL;
the principle of the preparation method is as follows: the surface of the ceria is reduced after the addition of the reducing agent, and then [ Pd (NH) is adsorbed 3 ) 2 ] 2+ And then after adsorption [ Pd (NH) ] 3 ) 2 ] 2+ The reduced ceria is oxidized such that palladium grows in situ on the ceria surface.
2. The method for preparing a supported palladium catalyst according to claim 1, wherein the reduction treatment is carried out by ultrasonic treatment.
3. The method for preparing the supported palladium catalyst according to claim 2, wherein the ultrasonic treatment time is 1 to 20 min.
4. The method for preparing a supported palladium catalyst as claimed in claim 1, wherein the solid obtained by separation after the treatment with the addition of the reducing agent is a reduced ceria, and the separation is performed by centrifugation, filtration, sedimentation or solvent evaporation.
5. The method of claim 1, wherein the ceria is synthesized by hydrothermal method.
6. A supported palladium catalyst obtained by the preparation method according to any one of claims 1 to 5.
7. Use of the supported palladium catalyst of claim 6 in the production of hydrogen from formaldehyde.
8. A method for producing hydrogen from formaldehyde, which comprises adding the supported palladium catalyst of claim 6 to a solution containing formaldehyde, and reacting at room temperature.
9. The method for producing hydrogen from formaldehyde according to claim 8, wherein the concentration of formaldehyde in the solution is 0.5 to 0.6 mol/L; the solution contains sodium hydroxide.
10. The method for producing hydrogen from formaldehyde according to claim 9, wherein the concentration of sodium hydroxide is 0.9 to 1.1 mol/L.
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