CN114602496A - Nano-carbon-loaded platinum-iron bimetallic catalyst, preparation method thereof and application thereof in CO selective oxidation reaction under hydrogen-rich atmosphere - Google Patents
Nano-carbon-loaded platinum-iron bimetallic catalyst, preparation method thereof and application thereof in CO selective oxidation reaction under hydrogen-rich atmosphere Download PDFInfo
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- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 42
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical compound [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 title claims abstract description 31
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
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- HPTLEXMXHIALNF-UHFFFAOYSA-L platinum(2+) dichlorate Chemical compound Cl(=O)(=O)[O-].[Pt+2].Cl(=O)(=O)[O-] HPTLEXMXHIALNF-UHFFFAOYSA-L 0.000 description 1
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
- C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
- C01B3/583—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being the selective oxidation of carbon monoxide
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0435—Catalytic purification
- C01B2203/044—Selective oxidation of carbon monoxide
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- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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Abstract
The invention discloses a nano-carbon supported platinum-iron bimetallic catalyst, a preparation method thereof and application thereof in CO selective oxidation reaction under a hydrogen-rich atmosphere, belonging to the technical field of catalysts. The catalyst takes nano-carbon as a carrier, and Pt and Fe are loaded on the surface of the nano-carbon carrier by a coprecipitation method to obtain the atomically dispersed Pt-Fe bimetallic catalyst. The load amount of Pt in the catalyst is 0.5-1 wt%, and the content of Fe is 0.1-0.3 wt%. The catalyst shows excellent catalytic performance in CO selective oxidation reaction under hydrogen-rich atmosphere, and can realize high selectivity and high conversion rate of CO at low temperature; and can maintain stable performance for a long time. The catalyst has low cost of raw materials and simple preparation process.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a nano-carbon supported platinum-iron bimetallic catalyst, a preparation method thereof and application thereof in CO selective oxidation reaction under a hydrogen-rich atmosphere.
Background
Hydrogen, as a renewable clean energy source, will play an increasingly important role in meeting the growing world's energy needs and avoiding the worse consequences of climate change. Proton Exchange Membrane Fuel Cells (PEMFCs) are considered as promising hydrogen utilization candidates because of their advantages such as high efficiency and low operating temperature. However, the platinum electrodes of proton exchange membrane fuel cells are easily poisoned by CO, further resulting in a loss of efficiency due to the presence of small amounts of residual toxic carbon monoxide gas in the industrial hydrogen production process of the hydrocarbon and water gas shift reaction. To remove residual CO prior to dosing hydrogen fuel gas into the PEMFC, a CO-preferential oxidation (PROX) reaction is considered a very attractive option, which can be achieved by selectively oxidizing CO in a hydrogen-rich atmosphere. However, achieving efficient oxidation of CO in PROX reactions at low temperatures remains challenging due to the lower PEMFC operating temperatures.
Among various supported metal catalysts developed, Platinum Group Metals (PGM), which are potential candidates for CO PROX reaction, have excellent activity and chemical stability. However, it is well known that single metal PGM catalysts on inert supports exhibit poor CO oxidation activity in PROX reactions, particularly at low, even ambient, temperatures, due to the strong adsorption of CO to O on the Pt surface2Activation is limited. In order to improve the catalytic performance of CO PROX at low temperatures, much research has been conducted on promoting PGM catalysts, particularly, on introducing a plurality of second-component reducing elements into PGM catalysts. It has now been found that PGM catalysts modified by the introduction of a second component generally exhibit higher low temperature oxidation activity in CO PROX reactions because the second component provides oxygen vacancies or reducible metal oxides/hydroxides as additional oxygen adsorption sites for reaction with CO. Nevertheless, in fact, the improved catalysts described above do not achieve the best utilization of platinum and another metal. The improved PGM catalysts prepared provide only a small number of interfacial sites for CO and O2The structure is not optimized to achieve maximum interface site density. In addition, only a few catalysts show good oxidation activity and selectivity at low temperature conditions, especially at room temperature, which is very important for the operating conditions of PEMFCs. Therefore, a build height is requiredThe active sites of the platinum-based bimetallic interface are dispersed and fully utilized to improve the low-temperature catalytic performance of the CO PROX reaction.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a nano-carbon supported platinum-iron bimetallic catalyst, a preparation method thereof and application thereof in CO selective oxidation reaction under a hydrogen-rich atmosphere, wherein the catalyst can realize high selectivity and high conversion rate of CO at low temperature; and can maintain stable performance for a long time.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a platinum iron bimetallic catalyst loaded by nano-carbon takes nano-carbon as a carrier, and Pt-Fe species are uniformly loaded on the surface of the nano-carbon carrier in an atomic cluster manner; wherein: noble metal Pt is an active component, and the content of the noble metal Pt is 0.5-1 wt%; fe is an auxiliary agent, and the content of the Fe is 0.1-0.3 wt%.
The nano carbon carrier is a graphene/nano diamond composite material, and the composite material is a core-shell structure formed by taking nano diamond as a core and taking graphene rich in defects as a shell; the platinum iron species are uniformly dispersed on the surface of the carrier in the form of atomic clusters by bonding with carbon atoms of the surface graphene defects.
The preparation method of the nano-carbon supported platinum-iron bimetallic catalyst comprises the following steps:
(1) mixing chloroplatinic acid and ferric nitrate solution to obtain metal salt solution, and loading platinum and iron on a nano-carbon carrier material by a coprecipitation method to obtain a nano-carbon loaded platinum-iron catalyst precursor;
(2) and placing the prepared solid precursor in a quartz tube, and carrying out reduction treatment in the mixed atmosphere of hydrogen and helium to obtain the nano-carbon loaded platinum-iron bimetallic catalyst.
In the step (1), the coprecipitation method comprises the following steps: firstly mixing a nano carbon carrier and water in a flask, uniformly dispersing the mixture by ultrasonic, placing the mixture in an oil bath kettle at the temperature of 80-100 ℃, and then sequentially adding sodium formate powder and a metal salt solution (the mass ratio of sodium formate to platinum is (300-350):1, the platinum loading is 0.5-1 wt%, and the iron loading is 0.1-0.3 wt%); keeping the temperature and stirring for 1-2 hours, standing and cooling to room temperature, and performing suction filtration and drying to obtain the nano-carbon supported platinum-iron catalyst precursor.
In the step (2), during the reduction process, H is in the mixed atmosphere2The volume ratio of the catalyst is 10 percent, the reduction temperature is 200-500 ℃, and the nano-carbon supported platinum-iron bimetallic catalyst is obtained after 1-2h of reduction.
The nano-carbon supported platinum-iron bimetallic catalyst is applied to CO selective oxidation reaction under a hydrogen-rich atmosphere, wherein the hydrogen-rich atmosphere is formed by CO and O2He and H2The composition is as follows: CO content of 0.5-1.0 vol.%, O2The volume content is 0.5-1.0 vol.%; the reaction temperature of the catalyst is 30-200 ℃, and the preferable reaction temperature is 30-120 ℃.
The invention has the following advantages: the invention firstly uses a platinum-iron bimetallic catalyst loaded by nano-carbon as a catalyst for CO selective oxidation reaction under hydrogen-rich atmosphere, and the catalyst is mainly obtained by depositing a metal salt solution containing platinum and iron on the surface of a nano-carbon material by a coprecipitation method. The preparation process has the advantages that Pt-Fe species can be uniformly dispersed on the surface of the nano carbon in the form of atomic clusters, and the optimization of Pt-Fe interface sites is realized. The catalyst shows excellent catalytic performance in CO selective oxidation reaction under hydrogen-rich atmosphere, and can realize high selectivity and high conversion rate of CO at low temperature; and can maintain stable performance for a long time. The catalyst has low cost of raw materials and simple preparation process.
Drawings
Fig. 1 is a scanning transmission electron microscope image of the nanocarbon-supported platinum-iron bimetallic catalyst of example 1.
FIG. 2 is a graph of CO conversion and CO selectivity for the CO selective oxidation reaction of the nanocarbon-supported platinum catalyst and the platinum-iron bimetallic catalyst in example 2 under a hydrogen-rich atmosphere; wherein: (a) conversion rate; (b) and (4) selectivity.
Fig. 3 is a graph of the stability of the nanocarbon-supported platinum-iron bimetallic catalyst of example 3 in a reaction atmosphere at a temperature of 30 ℃.
Detailed Description
The present invention is described in detail below with reference to the accompanying tables and examples.
In the following examples and comparative examples, the specific catalysts are represented by element symbols and English abbreviations, wherein Pt-platinum, Fe-iron, NDG-nanocarbon supports.
The preparation process of the nanocarbon supports in example 1 and comparative example 1 was as follows:
and (3) placing the nano-diamond raw material in an argon atmosphere of 80-100 mL/min at 900-1300 ℃ for roasting treatment for 3-4 h, and obtaining the nano-carbon carrier with the core-shell structure after roasting treatment.
Comparative example 1
Mixing nano carbon carrier powder and deionized water in a flask, stirring and carrying out ultrasound treatment for 30min to prepare suspension, placing the suspension in an oil bath kettle at 100 ℃, stirring for 30min, simultaneously adding sodium formate solid powder into the suspension, dropwise adding platinum chlorate solution (the mass ratio of sodium formate to platinum is 325.5:1, the platinum content is 0.75 wt%), stirring and refluxing for 1H, taking out the flask, cooling, standing for 8H, carrying out suction filtration, drying in a vacuum drying oven at 60 ℃ for 12H, and then adding 10% H2Reducing for 1h at 400 ℃ under the atmosphere of/He to obtain the platinum catalyst loaded by the nano carbon. It was noted as 0.75 Pt/NDG.
Example 1
Mixing nano carbon carrier powder and deionized water in a flask, stirring and carrying out ultrasound treatment for 30min to prepare suspension, placing the suspension in an oil bath kettle at 100 ℃, stirring for 30min, simultaneously adding sodium formate solid powder into the suspension, dropwise adding a metal salt solution (the mass ratio of sodium formate to platinum is 325.5:1, the platinum content is 0.75 wt%, and the iron content is 0.2 wt%), stirring and refluxing for 1H, taking out the flask, cooling and standing for 8H, carrying out suction filtration, drying in a vacuum drying oven at 60 ℃ for 12H, and then carrying out H extraction at 10 vol.% after drying in a vacuum drying oven at 10 ℃ for 10H2Reducing for 1h at 400 ℃ under the atmosphere of/He to obtain the nano-carbon loaded platinum-iron bimetallic catalyst. The scanning transmission electron microscope image of 0.75Pt0.2Fe/NDG is shown in FIG. 1, and it can be seen that Pt-Fe species are uniformly loaded on the surface of the nanocarbon carrier in the manner of atomic clusters.
Example 2
20mg of the catalyst obtained in comparative example 1 and example 1 was weighed and charged into a fixed bed reactor. Pretreatment of a catalyst: firstly at 10% H2Reducing the mixture for 1h at 400 ℃ in a He atmosphere, and then cooling the mixture to room temperature. The reaction atmosphere composition for the activity test was 1% CO + 0.5% O2+48％H2+ 50.5% He (volume ratio), reaction gas flow rate 15 ml/min. The catalyst was tested for activity at a temperature range of 30-200 c and the results are shown in figure 2. Wherein the catalytic performance of the 0.75Pt0.2Fe/NDG catalyst is superior to that of the 0.75Pt/NDG catalyst, and the high selectivity and the high conversion rate of CO at the room temperature of 30 ℃ can be realized.
Example 3
10mg of 0.75Pt0.2Fe/NDG catalyst is weighed and added into a fixed bed reactor, the reaction gas flow is 30ml/min, and the atmosphere composition is 1 percent of CO +0.5 percent of O2+48％H2+ 50.5% He (by volume), the reaction temperature was kept constant at 30 ℃ and the samples were tested continuously for 110 hours. The stability test results are shown in fig. 3, and it can be seen that the catalyst can maintain activity for a long time without significant deactivation.
The above examples are only for reference, and any technical solutions similar to the present invention or extending from the patent idea are within the protection scope of the present invention.
Claims (9)
1. A nano-carbon loaded platinum-iron bimetallic catalyst is characterized in that: the catalyst takes nano-carbon as a carrier, and Pt-Fe species are uniformly loaded on the surface of the nano-carbon carrier in an atomic cluster manner; wherein: noble metal Pt is used as an active component, and the content of Pt is 0.5-1 wt%; fe is taken as an auxiliary agent, and the content of Fe is 0.1-0.3 wt%.
2. The nanocarbon-supported platinum iron bimetallic catalyst as in claim 1, characterized in that: the nano-carbon carrier is a graphene/nano-diamond composite material, and the composite material is a core-shell structure formed by taking nano-diamond as a core and taking graphene rich in defects as a shell.
3. The nanocarbon-supported platinum iron bimetallic catalyst as in claim 2, characterized in that: the Pt-Fe species are uniformly dispersed on the surface of the carrier in the form of atomic clusters through bonding with carbon atoms of graphene defects on the surface of the carrier.
4. The method for preparing a nanocarbon-supported platinum-iron bimetallic catalyst as claimed in claim 1, characterized in that: the method comprises the following steps:
(1) mixing chloroplatinic acid and ferric nitrate solution to obtain metal salt solution, and loading platinum and iron on a nano-carbon carrier material by a coprecipitation method to obtain a nano-carbon loaded platinum-iron catalyst precursor;
(2) and placing the prepared nano-carbon-loaded platinum-iron catalyst precursor in a quartz tube, and carrying out reduction treatment in a mixed atmosphere of hydrogen and helium to obtain the nano-carbon-loaded platinum-iron bimetallic catalyst.
5. The method for preparing a nanocarbon-supported platinum-iron bimetallic catalyst as claimed in claim 4, characterized in that: in the step (1), the coprecipitation method comprises the following steps: mixing a nanocarbon carrier and water in a flask, uniformly dispersing the nanocarbon carrier and the water by ultrasonic waves, placing the nanocarbon carrier and the water in an oil bath pan at the temperature of between 80 and 100 ℃, and then sequentially adding sodium formate powder and a metal salt solution; keeping the temperature and stirring for 1-2 hours, standing and cooling to room temperature, and performing suction filtration and drying to obtain the nano-carbon supported platinum-iron catalyst precursor.
6. The method for preparing a nanocarbon-supported platinum-iron bimetallic catalyst as claimed in claim 5, characterized in that: in the step (1), in the process of the coprecipitation method, the platinum and iron content in the metal salt solution is configured according to the platinum and iron loading (the platinum loading is 0.5-1 wt%, and the iron loading is 0.1-0.3 wt%) in the catalyst; the mass ratio of the added sodium formate to the platinum in the metal salt solution is (300- & ltSUB- & gt 350- & gt) 1.
7. The method for preparing a nanocarbon-supported platinum-iron bimetallic catalyst as claimed in claim 4, characterized in that: in the step (2), the reduction processIn mixed atmosphere of H2The volume ratio is 10 percent, the reduction temperature is 200 ℃ and 500 ℃, and the reduction time is 1-2 h.
8. The use of the nanocarbon-supported platinum-iron bimetallic catalyst as claimed in claim 1 in CO selective oxidation reactions in a hydrogen-rich atmosphere, characterized in that: the catalyst is applied to CO selective oxidation reaction under hydrogen-rich atmosphere.
9. The use of the nanocarbon-supported platinum iron bimetallic catalyst in a CO selective oxidation reaction in a hydrogen-rich atmosphere according to claim 8, characterized in that: the hydrogen-rich atmosphere is composed of CO and O2He and H2The composition is as follows: CO content of 0.5-1.0 vol.%, O2The volume content is 0.5-1.0 vol.%; the reaction temperature of the catalyst is 30-200 ℃.
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