CN114832817B - Ultra-high Pt loading capacity sheet-shaped atomic-scale Pt/CeO 2 Catalyst and preparation method thereof - Google Patents
Ultra-high Pt loading capacity sheet-shaped atomic-scale Pt/CeO 2 Catalyst and preparation method thereof Download PDFInfo
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- 238000011068 loading method Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
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- 238000010438 heat treatment Methods 0.000 claims abstract description 26
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- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 150000000703 Cerium Chemical class 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
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- 239000005416 organic matter Substances 0.000 claims abstract description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 17
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- 239000008103 glucose Substances 0.000 claims description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 3
- 229930003268 Vitamin C Natural products 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 14
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 6
- 150000004706 metal oxides Chemical class 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 33
- 229910052697 platinum Inorganic materials 0.000 description 20
- 239000004005 microsphere Substances 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 6
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- 238000000034 method Methods 0.000 description 6
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- 229910000420 cerium oxide Inorganic materials 0.000 description 4
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- 238000000635 electron micrograph Methods 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 239000004471 Glycine Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 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
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a flaky atomic-scale Pt/CeO with ultrahigh Pt loading capacity 2 A catalyst comprising chloroplatinic acid, an organic matter containing reducing groups, and a cerium salt; the mass ratio of the organic matter containing the reducing group to the cerium salt is 0.1-2: 1. the preparation steps of the catalyst are as follows: dissolving chloroplatinic acid, organic matters and cerium salt in deionized water to obtain a mixed solution; atomizing the mixed solution, introducing the generated micro-fog drops into a tubular furnace for high-temperature treatment, and collecting orange-yellow powder at the other end of the tubular furnace; carrying out heat treatment on the orange powder, and removing residual organic matters to obtain the atomic-grade Pt/CeO with ultrahigh Pt loading capacity 2 A catalyst. Compared with the traditional metal oxide loaded atomic catalyst, the catalyst prepared by the invention has ultrahigh loading capacity of active metal Pt, still presents an atomic-level dispersion state at 10%, and has remarkably excellent catalytic water-vapor conversion performance on commercial CeO 2 Pt/CeO prepared by carrier 2 Catalyst and microspherical atomic Pt/CeO 2 A catalyst.
Description
Technical Field
The invention relates to the field of supported catalysts and heterogeneous catalysis, in particular to a sheet-shaped atomic-scale Pt/CeO (cerium oxide/cerium oxide) with ultrahigh Pt loading capacity 2 A catalyst and a preparation method thereof.
Background
Human development is not independent of the chemical industry, and catalysis is the "engine" of the chemical industry, and the core of the catalysis is the catalyst. The most widely used are supported catalysts, which consist essentially of an active metal and a support. In particular, noble metal catalyzed reactions are required, and supported catalysts both increase efficiency and reduce noble metal usage. The activity of the supported catalyst depends on the nature and number of active sites, the key influencing factor being the dispersion of the active metal. The dispersion characteristics not only determine the number of active sites and the atom utilization rate, but also influence the interfacial properties of the active metal/carrier. From the point of view of dispersion, supported catalysts are progressing towards atomically dispersed catalysts, which have only individual atoms isolated from one another as active centers.
Compared with nanometer level dispersion, the atomic level dispersion makes the utilization rate of active metal reach theoretical limit (100%), which is significant for reducing the use amount of noble metals such as Pt, pd and the like and the cost of the catalyst. For example, the efficiency of an atomic-scale catalyst is tens of times that of a nano-catalyst by electrocatalytic hydrogen evolution, oxygen reduction and other reactions. In order to obtain atomic-scale dispersion, the mass loading of the active metal is usually less than 3%, severely sacrificing the space for promoting the reactivity. Thus, a key common technical problem in the field of atomic scale catalysts is how to increase the loading of active metals. At present, the types of catalysts capable of realizing high-activity metal loading of more than 5% are only two types: porous carbon supported atomic-scale catalyst and metal sulfide supported atomic-scale catalyst. However, the application scenarios of carbon carriers and metal sulfide carriers are limited, and the carbon carriers and the metal sulfide carriers cannot be used in an oxidative reaction environment due to the problem of chemical stability. The use of metal oxide supports is only possible in an oxidizing environment. However, existing atomic scale catalyst preparation techniques cannot achieve atomic scale catalyst preparation with metal oxide loadings above 5%. Therefore, the invention of the metal oxide loaded high-load atomic-scale catalyst and the preparation technology thereof has important significance. Based on the method, the application provides flaky atomic-scale Pt/CeO with ultrahigh Pt loading capacity 2 A catalyst and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a flaky atomic-scale Pt/CeO with ultrahigh Pt loading capacity aiming at the problems and the defects in the prior art 2 Catalyst and preparation method thereof, and method for reducing CeO by adopting high temperature 2 The nano-sheets form defect sites, atomic-level metal Pt is deposited and anchored in situ, the atomic-level dispersion state is still presented when the loading amount reaches 10%, and the atomic-level dispersion state can be still maintained when the nano-sheets are heated to more than 400 ℃ in the air atmosphere.
In order to achieve the purpose, the invention adopts the following technical scheme:
ultra-high Pt loading capacity sheet-shaped atomic-scale Pt/CeO 2 A catalyst comprising chloroplatinic acid, an organic matter containing a reducing group, and a cerium salt; the mass ratio of the organic matter containing the reducing group to the cerium salt is 0.1-2: 1; the mol ratio of the chloroplatinic acid to the cerium salt is 0.01-0.2: 1.
further, the mass ratio of the organic matter containing a reducing group to the cerium salt is 0.25:1.
further, the reducing agent group comprises a hydroxyl group and/or an amino group.
Further, the organic matter comprises one or more of glucose, vitamin C and amino acid.
Further, the cerium salt includes cerium nitrate and/or cerium chloride.
The invention also provides a sheet-shaped atomic-grade Pt/CeO with ultrahigh Pt loading capacity 2 The preparation method of the catalyst comprises the following steps:
(1) Dissolving chloroplatinic acid, organic matters and cerium salt in deionized water to obtain a mixed solution;
(2) Atomizing the mixed solution prepared in the step (1), introducing the generated micro-mist drops into a tubular furnace for high-temperature reaction at 400-800 ℃, and collecting orange-yellow powder at the tail end of the tubular furnace;
(3) Carrying out heat treatment on the orange powder prepared in the step (2) to remove residual organic matters, thus obtaining the flaky atomic grade Pt/CeO with ultrahigh Pt loading capacity 2 A catalyst.
Further, the length of the heating zone of the tube furnace is 20-40 cm.
Further, the high-temperature reaction residence time in the step (2) is 2 to 3 seconds.
Further, the heat treatment temperature in the step (3) is 200-500 ℃.
Further, the length of the heating zone of the tube furnace is 30cm; the heat treatment temperature in the step (3) is 400 ℃.
Further, the heat treatment time in the step (3) is 1-3 h.
The flaky atomic-grade Pt/CeO with ultrahigh Pt loading capacity 2 The catalyst is applied to the field of hydrogen production by methanol reforming.
The invention has the advantages that:
(1) The invention utilizes the decomposition of cerium salt into CeO under the condition of high temperature 2 Nanosheets, with CeO 2 The nano-sheet is a carrier for in-situ deposition of atomic-scale Pt; the organic matter is decomposed at high temperature into reducing gas to reduce CeO 2 Nanosheets, forming a large number of surface defects, which become natural anchoring sites for Pt atoms; the finally formed nanosheet has a large specific surface area, and provides a sufficient anchoring surface for Pt atoms.
(2) The Pt loading capacity of the existing traditional metal oxide loaded atomic-scale catalyst is lower than 3%, and compared with the traditional metal oxide loaded atomic-scale catalyst, the catalyst prepared by the invention has ultrahigh active metal Pt loading capacity and still can present an atomic-scale dispersion state when being loaded by 10%.
(3) The monatomic catalyst obtained by the method is of a sheet structure, is beneficial to the mass transfer process of catalytic reaction, and improves the catalytic effect. Taking low-temperature water-vapor change reaction as an example, when the Pt loading capacity is equal to 8 percent, the flaky atomic-grade Pt/CeO (cerium oxide/cerium oxide) related to the invention 2 The activity of the catalyst is microsphere morphology atomic Pt/CeO 2 More than 2 times of the catalyst.
(4) CeO rich in defect sites in the invention 2 The ultrathin sheet has strong loading capacity and can realize the atomic-level dispersion of active metal Pt within the range of 0.1-10%. Commercial CeO 2 The upper limit of the loading of the single atom Pt by the nano particles is less than 5 percent.
(5) The catalyst prepared by the method has excellent performance, and when the low-temperature water vapor change reaction is taken as an example, the Pt loading capacity is 8 percent same, the atomic-scale Pt/CeO 2 Catalyst activity ratio commercial support preparationIs 5 times higher. And the stability of the catalyst is excellent. Taking the low-temperature water vapor change reaction as an example, when the Pt loading capacity is 5 percent the same, the atomic-scale Pt/CeO related by the invention 2 The atomic-level dispersion state of Pt is almost unchanged after the catalyst is catalyzed, and Pt almost completely agglomerates into metal nano particles after the catalyst prepared by a commercial carrier is catalyzed.
Drawings
FIG. 1 is the atomic scale 8% of Pt/CeO obtained in example 1 of the present invention 2 (a) A scanning electron micrograph;
FIG. 2 is a comparison of 8% Pt/CeO of comparative example 1 commercial Carrier preparation of the present invention 2 A scanning electron micrograph of catalyst (b);
FIG. 3 is the atomic scale 10% of Pt/CeO obtained in example 3 of the present invention 2 (a) Spherical aberration electron micrographs of;
FIG. 4 is a comparative 5% Pt/CeO of comparative example 1 commercial Carrier preparation of the invention 2 Catalyst-spherical aberration electron micrograph of commercial (b);
FIG. 5 shows the atomic-scale 8% of Pt/CeO obtained in example 1 of the present invention 2 Comparison with comparative example 2 commercial support preparation 5% 2 Catalyst-commercial X-ray absorption spread spectrum (a) contrast plot;
FIG. 6 is the atomic scale 8% of Pt/CeO obtained in example 1 of the present invention 2 Comparison with comparative example 2 commercial support preparation 5% 2 Catalyst-commercial X-ray photoelectron spectroscopy (b) comparison;
FIG. 7 shows atomic 5% of Pt/CeO obtained in example 2 of the present invention 2 (a) Comparative example 5% preparation of commercial Carrier 2 Catalyst-commercial (b) catalytic water vapor shift performance comparison plot;
FIG. 8 shows atomic 5% of Pt/CeO obtained in example 2 of the present invention 2 (a) Comparative example 5% preparation of commercial Carrier 2 Catalyst-comparative X-ray photoelectron spectroscopy after commercial (b) catalyzed water-gas shift reaction;
FIG. 9 shows the atomic-scale 8% of Pt/CeO obtained in example 1 of the present invention 2 (a) Scanning electron microscopy images of (a);
FIG. 10 is a comparative example 3 of the present invention obtained without adding an organic matter 8% of Pt/CeO 2 Scanning electron microscopy of catalyst-microsphere (b);
FIG. 11 shows the atomic-scale 8% of Pt/CeO obtained in example 1 of the present invention 2 (a) Comparison with comparative example 3 obtained without addition of organic substance 8% of Pt/CeO 2 The catalytic water-vapor conversion performance of the catalyst-microsphere (b) is compared with that of the microsphere (b).
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Of course, the described embodiments are only some embodiments of the invention, and not all embodiments.
Example 1
This example provides an ultra-high Pt loading atomic grade Pt/CeO 2 The preparation method of the catalyst comprises the following steps:
step 1: dissolving 0.14mmol of chloroplatinic acid, 2mmol of cerium nitrate and 0.2g of glucose in deionized water to form a mixed solution of 30 mL;
step 2: pouring the mixed solution into an atomizer, introducing the generated micro-fog drops into a tubular furnace for high-temperature treatment, wherein the length of a heating area of the tubular furnace is 30cm, the temperature is 600 ℃, and collecting orange yellow powder at the other end of the tubular furnace;
and step 3: subjecting the orange-yellow powder to a heat treatment at 400 deg.C to remove residual organics for 2 hours to obtain an atomic-scale Pt/CeO content of 8% 2 A catalyst.
Example 2
This example provides an ultra-high Pt loading atomic grade Pt/CeO 2 The preparation method of the catalyst comprises the following steps:
step 1: dissolving 0.09mmol of chloroplatinic acid, 2mmol of cerium nitrate and 0.2g of glucose in deionized water to form a mixed solution of 30 mL;
step 2: pouring the mixed solution into an atomizer, introducing the generated micro-fog drops into a tubular furnace for high-temperature treatment, wherein the length of a heating area of the tubular furnace is 30cm, the temperature is 600 ℃, and collecting orange yellow powder at the other end of the tubular furnace;
step (ii) of3: subjecting the orange-yellow powder to a heat treatment at 400 deg.C to remove residual organics for 2 hours to obtain an atomic-scale Pt/CeO content of 5% 2 A catalyst.
Example 3
This example provides an ultra-high Pt loading atomic grade Pt/CeO 2 The preparation method of the catalyst comprises the following steps:
step 1: dissolving 0.18mmol of chloroplatinic acid, 2mmol of cerium nitrate and 0.2g of glucose in deionized water to form a mixed solution of 30 mL;
step 2: pouring the mixed solution into an atomizer, introducing the generated micro-fog drops into a tubular furnace for high-temperature treatment, wherein the length of a heating area of the tubular furnace is 30cm, the temperature is 700 ℃, and collecting orange yellow powder at the other end of the tubular furnace;
and step 3: subjecting the orange-yellow powder to a heat treatment at a temperature of 400 deg.C to remove residual organics for 2 hours to obtain an atomic level of Pt/CeO of 10% Pt loading 2 A catalyst.
Example 4
This example provides an ultra-high Pt loading atomic-scale Pt/CeO 2 The preparation method of the catalyst comprises the following steps:
step 1: dissolving 0.14mmol of chloroplatinic acid, 2mmol of cerium nitrate and 0.2g of glucose in deionized water to form a mixed solution of 30 mL;
step 2: pouring the mixed solution into an atomizer, introducing the generated micro-fog drops into a tubular furnace for high-temperature treatment, wherein the length of a heating area of the tubular furnace is 30cm, the temperature is 600 ℃, and collecting orange yellow powder at the other end of the tubular furnace;
and step 3: subjecting the orange-yellow powder to a heat treatment at 300 deg.C to remove residual organics for 2 hours to obtain an atomic-scale Pt/CeO content of 8% 2 A catalyst.
Example 5
This example provides an ultra-high Pt loading atomic grade Pt/CeO 2 The preparation method of the catalyst comprises the following steps:
step 1: dissolving 0.14mmol of chloroplatinic acid, 2mmol of cerium nitrate and 0.2g of vitamin C in deionized water to form a mixed solution of 30 mL;
step 2: pouring the mixed solution into an atomizer, introducing the generated micro-fog drops into a tubular furnace for high-temperature treatment, wherein the length of a heating area of the tubular furnace is 30cm, the temperature is 600 ℃, and collecting orange yellow powder at the other end of the tubular furnace;
and step 3: subjecting the yellow-orange powder to a heat treatment at a temperature of 350 deg.C to remove residual organics for 2 hours to obtain an atomic level Pt/CeO of 8% Pt loading 2 A catalyst.
Example 6
This example provides an ultra-high Pt loading atomic-scale Pt/CeO 2 The preparation method of the catalyst comprises the following steps:
step 1: dissolving 0.14mmol of chloroplatinic acid, 2mmol of cerium chloride and 0.2g of glucose in deionized water to form a mixed solution of 30 mL;
and 2, step: pouring the mixed solution into an atomizer, introducing the generated micro-fog drops into a tubular furnace for high-temperature treatment, wherein the length of a heating area of the tubular furnace is 30cm, the temperature is 600 ℃, and collecting orange yellow powder at the other end of the tubular furnace;
and step 3: subjecting the orange-yellow powder to a heat treatment at a temperature of 400 deg.C to remove residual organics for 2 hours to obtain an atomic level Pt/CeO of 8% Pt loading 2 A catalyst.
Example 7
Step 1: dissolving 0.14mmol of chloroplatinic acid, 2mmol of cerium nitrate and 0.2g of glycine in deionized water to form a 30mL mixed solution;
and 2, step: pouring the mixed solution into an atomizer, introducing the generated micro-fog drops into a tubular furnace for high-temperature treatment, wherein the length of a heating area of the tubular furnace is 30cm, the temperature is 600 ℃, and collecting orange yellow powder at the other end of the tubular furnace;
and step 3: heat treating the orange powder at 400 deg.C to remove residual organic matter for 2 hr to obtain the final productTo 8% Pt loading of atomic grade Pt/CeO 2 A catalyst.
Comparative example 1
For comparison, commercial CeO was used 2 Preparation of the support 8% Pt/CeO 2 The catalyst comprises the following steps:
step 1:0.14mmol of chloroplatinic acid was dissolved in 1mL of deionized water, and 2mmol of commercial CeO was added 2 Carrier powder (alatin), stirred until dry;
and 2, step: drying the above dry powder in an oven at 80 deg.C for 5-6 hr, and heat treating at 400 deg.C for 2 hr to obtain a Pt/CeO content of 8% 2 Catalyst-commercial.
Comparative example 2
For comparison, commercial CeO was used 2 Preparation of the support 8% Pt/CeO 2 The catalyst comprises the following steps:
step 1:0.09mmol of chloroplatinic acid was dissolved in 1mL of deionized water, and 2mmol of commercial CeO was added 2 Carrier powder (alatin), stirred until dry;
step 2: drying the above dry powder in an oven at 80 deg.C for 5-6 hr, and heat treating at 400 deg.C for 2 hr to obtain a Pt/CeO fraction of 5% 2 Catalyst-commercial.
Comparative example 3
For comparison, preparation of 8% Pt/CeO without adding any organic matter 2 The catalyst comprises the following steps:
step 1: dissolving 0.14mmol of chloroplatinic acid and 2mmol of cerous nitrate in deionized water to form a 30mL mixed solution;
step 2: pouring the mixed solution into an atomizer, introducing the generated micro-fog drops into a tubular furnace for high-temperature treatment, wherein the length of a heating area of the tubular furnace is 30cm, the temperature is 600 ℃, and collecting orange yellow powder at the other end of the tubular furnace;
and 3, step 3: subjecting the above orange-yellow powder to a heat treatment at 400 ℃ for 2 hours to remove residual organics, to obtain a comparative 8% Pt/CeO 2 Catalyst-microspheres.
To obtain the ultra-high Pt loading atomic-scale Pt/CeO 2 The hydrogen production performance data of the catalyst by the water-vapor shift reaction is implemented as follows:
step 1: mixing 100mg of catalyst powder with 3mL of quartz sand, filling the mixture into a quartz tube with the inner diameter of 8mm to form a catalyst bed layer, and placing the catalyst bed layer into a reaction furnace;
and 2, step: at 3% of H 2 The yield rate of hydrogen was measured at a temperature gradient of 10 ℃ in a temperature range of 160 to 260 ℃ under a normal pressure mixed reaction atmosphere of Ar at a rate of 87% CO + O + CO + and a gas flow rate of 25 mL/min. The composition of the tail gas is analyzed on line by gas chromatography, and the quantification of the hydrogen is calibrated by standard gas with two concentrations of 0.5 percent and 2.0 percent.
FIG. 1 shows the atomic-scale 8% of Pt/CeO obtained in example 1 of the present invention 2 (a) Scanning electron micrographs; FIG. 2 is a comparison of 8% Pt/CeO of comparative example 1 commercial Carrier preparation of the present invention 2 A scanning electron micrograph of catalyst (b);
by comparison, it can be seen that the atomic scale of 8% Pt/CeO was obtained in example 1 of the present invention 2 The catalyst is of a flake structure, has a large specific surface area, and can load more monatomic sites. 8% of Pt/CeO obtained in comparative example 1 2 The catalyst-commercially is irregular nano-particles, is easy to agglomerate, and is not beneficial to the loading and the stability of the single atom sites.
FIG. 3 shows the atomic 10% of Pt/CeO obtained in example 3 of the present invention 2 (a) Spherical aberration electron micrographs of; FIG. 4 is a comparative 5% Pt/CeO prepared using the commercial support of comparative example 1 of the present invention 2 Catalyst-spherical aberration electron micrograph of commercial (b);
by comparison, it can be seen that the atomic scale 10% Pt/CeO obtained in example 1 of the present invention 2 Pt in the catalyst is monoatomic dispersion (circled marks). 5% Pt/CeO obtained in comparative example 1 due to the limited load Capacity 2 Catalyst-commercial Pt is nano-scale dispersed (circled marks) which is not conducive to the utilization of precious metals.
FIG. 5 shows the atomic-scale 8% of Pt/CeO obtained in example 1 of the present invention 2 Comparison with comparative example 2 commercial support preparation 5% 2 Catalyst-commercial X-ray absorption spread spectrum (a) contrast plot; FIG. 6 is a drawing of the present inventionAtomic scale 8% of Pt/CeO obtained in example 1 2 Comparative example 5% preparation of commercial Carrier 2 Catalyst-commercial X-ray photoelectron spectroscopy (b) comparison;
as can be seen from a comparison of FIG. 5, the atomic scale of 8% Pt/CeO obtained in example 1 of the present invention 2 The Pt in the catalyst is all coordinated by Pt-O, which is illustrated as a monoatomic dispersion, while the comparative example is Pt/CeO 2 Catalyst-commercial occurrence of Pt-Pt bond coordination, indicating the presence of Pt nanoparticles, is consistent with the results expressed in figure 2.
As can be seen from a comparison of FIG. 6, the atomic scale of 8% Pt/CeO obtained in example 1 of the present invention 2 The Pt in the catalyst was well dispersed and all were in a combined state. Comparative examples Pt/CeO with lower Pt loading (5%) due to limited load Capacity 2 Catalyst-commercial agglomeration of part of the Pt to the metallic state has occurred, resulting in a loss of Pt utilization and a decrease in activity.
FIG. 7 shows atomic 5% of Pt/CeO obtained in example 2 of the present invention 2 (a) Comparative example 5% preparation of commercial Carrier 2 Catalyst-commercial (b) catalytic water vapor shift performance comparison plot;
as can be seen from the figure, the atomic 5% of Pt/CeO obtained by the present invention 2 Comparative 5% of the Performance of the catalyst significantly better than that of the comparative commercial support preparation 2 Catalyst-commercial.
FIG. 8 is the atomic scale 5% of Pt/CeO obtained in example 2 of the present invention 2 (a) Comparative example 5% preparation of commercial Carrier 2 Catalyst-comparative X-ray photoelectron spectroscopy after commercial (b) catalyzed water-gas shift reaction;
as can be seen from the figure, the atomic 5% of Pt/CeO obtained by the present invention 2 Comparative 5% of the catalyst stability significantly better than that of the comparative commercial support preparation 2 Catalyst-commercial. Wherein the atomic ratio of Pt/CeO obtained by the invention is 5% 2 The state of Pt of the catalyst after the catalytic reaction remained in the monoatomic combination state, while the comparative example prepared on the commercial support had a content of 5% Pt/CeO 2 Catalyst-commercial Pt aggregates into metal nanoparticles after catalytic reaction.
FIG. 9 is a drawing of the present inventionAtomic scale 8% of Pt/CeO obtained in example 1 2 (a) Scanning electron micrographs of (a); FIG. 10 shows the comparative example 3 of the present invention obtained without adding an organic substance, in which Pt/CeO was 8% 2 Scanning electron microscopy of catalyst-microsphere (b);
as can be seen, glucose is critical to the sheeting result, and if no glucose is added, the microsphere morphology of the comparative example is formed.
FIG. 11 shows the atomic-scale 8% of Pt/CeO obtained in example 1 of the present invention 2 (a) Comparison with that obtained in comparative example 3 with no organic addition 8% 2 The catalytic water-vapor conversion performance of the catalyst-microsphere (b) is compared with that of the microsphere (b).
As can be seen from the figure, the performance of the flaky, atomically 8% Pt/CeO2 catalyst obtained in the present invention was significantly better than the comparative example 8% 2 Catalyst-microspheres. Improving the morphology of the catalyst by the introduction of glucose has a positive effect on the performance.
The applicant states that the product and the detailed preparation method of the present invention are illustrated by the above examples, but the present invention is not limited to the above product and the detailed preparation method, i.e. the present invention is not meant to be implemented by relying on the above product and the detailed preparation method. It should be understood by those skilled in the art that any modification of the present invention, equivalent replacement of the raw materials and addition of auxiliary materials, selection of specific modes, etc., of the product of the present invention, fall within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical idea of the present invention. These simple variants are all within the scope of protection of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (9)
1. Ultra-high Pt-loading sheet atomic-level Pt/CeO 2 The catalyst is characterized in that raw materials comprise chloroplatinic acid, organic matters containing reducing groups and cerium salt; the mass ratio of the organic matter containing the reducing group to the cerium salt is 0.1-2; the mol ratio of the chloroplatinic acid to the cerium salt is 0.01-0.2: 1;
the preparation method of the catalyst comprises the following steps:
(1) Dissolving chloroplatinic acid, organic matters and cerium salt in deionized water to obtain a mixed solution;
(2) Atomizing the mixed solution prepared in the step (1), introducing the generated micro-fog drops into a tubular furnace for high-temperature reaction at 400-800 ℃, and collecting orange-yellow powder at the tail end of the tubular furnace;
(3) Carrying out heat treatment on the orange powder prepared in the step (2) to remove residual organic matters, thus obtaining the flaky atomic grade Pt/CeO with ultrahigh Pt loading capacity 2 A catalyst.
2. The ultra-high Pt loading platelet-shaped atomic grade Pt/CeO of claim 1 2 Catalyst, characterized in that the reducing group comprises a hydroxyl group and/or an amino group.
3. The ultra-high Pt loading platelet-shaped atomic grade Pt/CeO of claim 2 2 The catalyst is characterized in that the organic matter comprises one or more of glucose, vitamin C and amino acid.
4. The ultra-high Pt loading platelet-shaped atomic grade Pt/CeO of claim 1 2 Catalyst, characterized in that said cerium salt comprises cerium nitrate and/or cerium chloride.
5. The ultra-high Pt loading platelet-shaped atomic grade Pt/CeO of claim 1 2 The catalyst is characterized in that the length of the heating zone of the tubular furnace is 20-40 cm.
6. The ultra-high Pt loading platelet-shaped atomic grade Pt/CeO of claim 1 2 The catalyst is characterized in that the high-temperature reaction retention time in the step (2) is 2-3 seconds.
7. The ultra-high Pt loading platelet-shaped atomic grade Pt/CeO of claim 1 2 The catalyst is characterized in that the heat treatment temperature in the step (3) is 200-500 ℃.
8. The ultra-high Pt loading platelet-shaped atomic grade Pt/CeO of claim 1 2 The catalyst is characterized in that the heat treatment time in the step (3) is 1-3 h.
9. Use of the catalyst according to claims 1-8, wherein the ultra-high Pt loading is in the form of platelet-shaped atomic grade Pt/CeO 2 The catalyst is applied to the field of hydrogen production by methanol reforming.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903731A (en) * | 2005-07-26 | 2007-01-31 | 中国科学院物理研究所 | Flower shape structured nano-cerium oxide and its preparation method and use |
| CN105585043A (en) * | 2016-03-11 | 2016-05-18 | 九江学院 | Preparation method of flowerlike cerium oxide nano-material |
| CN106794448A (en) * | 2014-10-07 | 2017-05-31 | 巴斯夫公司 | The synthesis of the colloid noble metal nano particles with controlled size and form |
| CN108855071A (en) * | 2018-07-12 | 2018-11-23 | 杭州晟睿新材料有限公司 | A kind of preparation method and applications of cerium oxide support type high-dispersion nano catalyst |
| CN109999802A (en) * | 2019-04-15 | 2019-07-12 | 西安交通大学 | A kind of monatomic platinum based catalyst of high stability and preparation method thereof and the application in volatility oxygen-containing hydrocarbon low temperature purification |
| CN113856723A (en) * | 2021-09-27 | 2021-12-31 | 华东理工大学 | Metal atom catalyst and preparation method thereof |
-
2022
- 2022-04-27 CN CN202210454495.XA patent/CN114832817B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903731A (en) * | 2005-07-26 | 2007-01-31 | 中国科学院物理研究所 | Flower shape structured nano-cerium oxide and its preparation method and use |
| CN106794448A (en) * | 2014-10-07 | 2017-05-31 | 巴斯夫公司 | The synthesis of the colloid noble metal nano particles with controlled size and form |
| CN105585043A (en) * | 2016-03-11 | 2016-05-18 | 九江学院 | Preparation method of flowerlike cerium oxide nano-material |
| CN108855071A (en) * | 2018-07-12 | 2018-11-23 | 杭州晟睿新材料有限公司 | A kind of preparation method and applications of cerium oxide support type high-dispersion nano catalyst |
| CN109999802A (en) * | 2019-04-15 | 2019-07-12 | 西安交通大学 | A kind of monatomic platinum based catalyst of high stability and preparation method thereof and the application in volatility oxygen-containing hydrocarbon low temperature purification |
| CN113856723A (en) * | 2021-09-27 | 2021-12-31 | 华东理工大学 | Metal atom catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Dispersion and support dictated properties and activities of Pt/metal oxide catalysts in heterogeneous CO oxidation;Jiaojiao Song等;《Nano Research》;20210504;第14卷;第4842页右栏第2节，第4842页左栏最后一段，第4846页左栏第一段 * |
| Jiayu Chen等.Surface Engineering Protocol To Obtain an Atomically Dispersed Pt/CeO2 Catalyst with High Activity and Stability for CO Oxidation.《ACS Sustainable Chemistry & Engineering》.2018,第6卷14054-14062页. * |
| Surface Engineering Protocol To Obtain an Atomically Dispersed Pt/CeO2 Catalyst with High Activity and Stability for CO Oxidation;Jiayu Chen等;《ACS Sustainable Chemistry & Engineering》;20180917;第6卷;摘要，第14055页左栏倒数两段，第14055页右栏第3段 * |
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