CN111282590B - Metal monatomic-loaded nitrogen-doped porous graphene composite catalyst and preparation method thereof - Google Patents
Metal monatomic-loaded nitrogen-doped porous graphene composite catalyst and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 239000010931 gold Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Chemical class 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical class [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052742 iron Chemical class 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 9
- 238000011068 loading method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000011049 filling Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- -1 salt compounds Chemical class 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 238000004108 freeze drying Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 1
- 238000000137 annealing Methods 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002211 ultraviolet spectrum 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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Abstract
The invention belongs to the field of catalysts, and discloses a preparation method of a nitrogen-doped porous graphene-supported metal monoatomic composite catalyst, which comprises the steps of firstly taking graphene oxide, hydrogen peroxide solution and ammonia water as main raw materials, and performing hydrothermal reaction to synthesize nitrogen-doped porous graphene; then introducing a metal salt solution, and further reacting to realize the synthesis and loading of metal monoatoms in the nitrogen-doped porous graphene. The preparation process of the composite catalyst can be effectively simplified by improving the whole process flow and the reaction conditions and parameters of each key process, and the dispersibility of metal single atoms and the catalyst activity can be effectively improved, so that the preparation process is suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a metal single-atom-supported nitrogen-doped porous graphene composite catalyst and a preparation method thereof.
Background
Graphene has a unique graphitized planar structure, a high specific surface area, good conductivity and other excellent properties, so that the graphene becomes an ideal carrier of the catalyst. The catalytic activity of graphene can be further enhanced by processing and assembling the flakes such that the resulting material has pores that bind to more exposed active sites. The porous structure of the graphene sheet then results in it having more exposed catalytically active edge sites; and the doped nitrogen atom is at sp 2 The hybrid carbon skeleton causes charge delocalization, so that the density of states of adjacent C atoms at the Fermi level is increased, and the catalytic activity of the hybrid carbon skeleton can be further improved [ Facile synthesis of porous nitrogen-doped holey graphene as an efficient metal-free catalyst for the oxygen reduction reaction. Nano Research,2017,10 (1): 305-319 ].]. Furthermore, due to the modulation of chemical properties, the doping of heteroatoms into the carbon network of graphene can enhance catalytic activity by forming new active sites.
SAC shows excellent activity, stability and selectivity in catalytic reactions due to the high dispersion of active components in single-atom catalysts (SAC), a great improvement in metal utilization efficiency, and the interaction of active centers with adjacent coordinating atoms. Therefore, efficient synthesis and application of SAC is a very important research direction in the field of catalysis and materials research in recent years [ Cascade anchoring strategy for general mass production of high-loading single-atom metal-potential technologies, nature communications,2019,10,1278 ]. The single-atom catalyst combines the advantages of heterogeneous catalysts and homogeneous catalysts, and overcomes the defects between the heterogeneous catalysts and the homogeneous catalysts: compared with heterogeneous catalysts, SAC improves the utilization rate of atoms to the greatest extent, and has uniform active sites and adjustable electronic environment so as to realize high catalytic activity and selectivity; while having higher stability and better recyclability than homogeneous catalysts.
However, due to the strong tendency of the single-atom catalyst to migrate and aggregate active atoms during the manufacturing process or subsequent application, SAC controllability is still very challenging, and loading single atoms on a suitable carrier is an effective method to achieve SAC controllable loading. The section of los Angeles division of California university teaches that a series of metal monoatomic catalysts [ General synthesis and definitive structural identification of MN ] are prepared by hydrothermally assembling graphene oxide, a metal precursor and hydrogen peroxide, and then annealing at high temperature (900 ℃) in an ammonia atmosphere 4 C 4 single-atom catalysts with tunable electrocatalytic activities,Nature Catalysis,2018,1,63-72]. However, the method involves ammonia gas and high temperature treatment, has harsh conditions, is difficult to realize large-scale preparation, and is mainly suitable for the field of electrocatalysis. Patent CN106513029a discloses a synthesis process for loading metal nanoparticles on a nitrogen-doped porous graphene material by one-pot one-step reaction; however, the method is carried with nano-particles, metal monoatoms cannot be obtained, and the catalytic performance is limited. Therefore, a simple, efficient and easily-scaled preparation method based on the single-atom catalyst is developed, and has important research and application values.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the nitrogen-doped porous graphene supported composite catalyst for supporting metal monoatoms, realizes the loading of the nitrogen doping and the metal monoatoms while constructing a graphene porous structure, and has the advantages of simple preparation process, low requirement on equipment and suitability for popularization and application.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the metal-monoatomic-supported nitrogen-doped porous graphene composite catalyst comprises the following steps of:
1) Synthesis of nitrogen doped porous graphene: adding a hydrogen peroxide (porogen) solution and a nitrogen source into the graphene oxide aqueous solution, uniformly mixing, and then heating to perform hydrothermal reaction to obtain nitrogen doped porous graphene (NHG);
2) Synthesis of monoatomic catalyst: and uniformly dispersing the obtained nitrogen-doped porous graphene in water, then adding a metal salt solution into the obtained dispersion liquid, and stirring for reaction in a dark place to obtain the metal-monoatomic-loaded nitrogen-doped porous graphene composite catalyst.
In the scheme, the concentration of the graphene oxide aqueous solution is 1-10mg/mL.
In the above scheme, the concentration of the hydrogen peroxide solution is 0.2-30wt.%.
In the above scheme, the nitrogen source is ammonia water.
In the scheme, the mass ratio of the graphene oxide to the hydrogen peroxide to the ammonia introduced in the step 1) is 1 (0.045-5) to 0.05-30.
In the scheme, the hydrothermal reaction temperature is 100-220 ℃ and the time is 5-24 hours.
In the scheme, the concentration of the nitrogen-doped porous graphene in the dispersion liquid in the step 2) is 0.5-5mg/mL.
In the above scheme, the metal salt is one or more of water-soluble salt compounds of palladium, cobalt, gold, platinum or iron.
In the above scheme, the mass ratio of NHG to water-soluble salt compound in the step 2) is 100 (0.3-14).
In the scheme, the light-shielding stirring reaction temperature is 0-10 ℃ and the time is more than 1 h.
The nitrogen-doped porous graphene composite catalyst loaded with metal monoatoms prepared according to the scheme has the advantages of porous structure, large specific surface area, high nitrogen doping amount, high dispersity of metal monoatoms, water phase dispersibility and the like.
Compared with the prior art, the invention has the beneficial effects that:
1) The synthesis process is simple, the preparation process does not need reducing agent, and the production efficiency is high;
2) The reaction condition is mild, the required raw materials are simple and easy to obtain, special or complex reaction equipment is not needed, the requirement on the reaction equipment is low, the energy consumption is low, the preparation cost can be effectively reduced, and the industrial popularization is easy;
3) The obtained composite material has the advantages of large specific surface area, high catalytic activity, good water phase dispersibility and the like;
4) The metal monoatoms can form a coordination structure with nitrogen doped in the nitrogen doped porous graphene carrier, so that chemical bonding force is generated to anchor the monoatoms, and the stability of the metal monoatoms is effectively improved; in addition, the electronic property of the metal monoatomic is regulated and controlled through coordination with the N atom, so that the catalytic performance of the metal monoatomic can be further effectively improved.
Drawings
FIG. 1 is a schematic diagram of a preparation flow of a composite catalyst according to the present invention;
FIG. 2 is a scanning electron microscope image of the Pd1/NHG composite catalyst obtained in example 1 of the present invention;
FIG. 3 is a high angle annular dark field-scanning transmission electron microscope image of the Pd1/NHG composite catalyst obtained in example 1 of the present invention;
FIG. 4 is an energy spectrum and an elemental surface scanning diagram of the Pd1/NHG composite catalyst obtained in example 1 of the present invention;
FIG. 5 is a photoelectron spectrum of the Pd1/NHG composite catalyst obtained in example 1 of the present invention;
FIG. 6 is a UV spectrum of the Pd1/NHG complex catalyst of example 1 of the present invention for reducing 4-nitrophenol by sodium borohydride.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the following examples, graphene oxide was used as a self-made product of the Hummers method [ Preparation of Graphitic oxide. Journal of the American Chemical Society,1958,208,1334-1339 ].
In the following embodiments, a preparation flow chart of the metal-monoatomic-supported nitrogen-doped porous graphene composite catalyst is shown in fig. 1, and specifically includes the following steps:
firstly, preparing a graphene oxide aqueous solution, adding a hydrogen peroxide solution with the concentration of 0.2-30wt.% and ammonia water with the concentration of 28-30wt.% into the graphene oxide aqueous solution, uniformly mixing, heating the obtained mixture to 100-220 ℃ for hydrothermal reaction for 5-24 hours, and obtaining nitrogen-doped porous graphene; wherein the mass ratio of graphene oxide to hydrogen peroxide to ammonia is 1 (0.045-5) (0.05-30);
and dispersing the obtained nitrogen-doped porous graphene in deionized water to prepare nitrogen-doped porous graphene aqueous dispersion with the concentration of 0.5-5mg/mL, and then adding a metal precursor salt solution into the dispersion at the temperature of 0-10 ℃ to react for more than 1 hour under light-shielding stirring to obtain the composite catalyst.
Example 1
The preparation method of the Pd single-atom-loaded nitrogen-doped porous graphene composite catalyst (Pd 1/NHG) comprises the following steps:
1) Synthesis of nitrogen doped porous graphene (NHG): feeding graphene oxide, hydrogen peroxide and ammonia according to a mass ratio of 1:0.05:0.05; taking 75mL of graphene oxide aqueous solution with the concentration of 1mg/mL, filling the graphene oxide aqueous solution into a 100mL polytetrafluoroethylene reaction kettle liner, adding 1.875mL of hydrogen peroxide solution with the mass fraction of 0.2% and 0.0125mL of ammonia water solution with the mass fraction of 28% into the mixture, uniformly mixing, filling the obtained mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 24 hours in a baking oven at the temperature of 100 ℃ to obtain nitrogen-doped porous graphene (NHG);
2) Synthesis of composite catalyst: NHG and potassium palladium chloride are added according to the mass ratio of 1:0.003; 50mg of NHG is ultrasonically dispersed in 100mL of deionized water to prepare an aqueous dispersion of NHG with the concentration of 0.5mg/mL, then 0.15mg of potassium palladium chloride is added into the aqueous dispersion in the temperature environment of ice bath (0 ℃), the mixture is stirred and reacted for 1h in a dark place, and the Pd1/NHG composite catalyst is obtained after suction filtration and freeze-drying.
The scanning electron microscope image and the transmission electron microscope image of the Pd1/NHG composite catalyst obtained in the embodiment are respectively shown in fig. 2 and 3, and the result shows that: the prepared Pd1/NHG composite catalyst has a porous structure and is loaded with uniformly dispersed metal monoatoms.
The component characterization results of the Pd1/NHG composite catalyst obtained in the embodiment are respectively shown in fig. 4, fig. 5 and table 1, and the results show that: the resulting catalyst contained up to 9.07% of N atom content and was successfully loaded with metallic palladium, with Pd atom content of 0.36% (XPS).
Table 1 elemental content analyzed by XPS
The Pd1/NHG composite catalyst obtained in the example has a Pd content of 2.0wt.%; in the catalytic reduction reaction of the p-nitrophenol, the catalytic efficiency (conversion frequency) is 1915.2min -1 。
Example 2
The preparation method of the Pt single-atom-loaded nitrogen-doped porous graphene composite catalyst (Pt 1/NHG) comprises the following steps:
1) Synthesis of nitrogen doped porous graphene (NHG): feeding graphene oxide, hydrogen peroxide and ammonia according to a mass ratio of 1:5:30; taking 40mL of graphene oxide aqueous solution with the concentration of 1mg/mL, filling the graphene oxide aqueous solution into a 100mL polytetrafluoroethylene reaction kettle liner, adding 6.67mL of hydrogen peroxide solution with the mass fraction of 30% and 40mL of ammonia water solution with the mass fraction of 28% into the mixture, uniformly mixing the mixture, filling the obtained mixture into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 5h in a 220 ℃ oven to obtain nitrogen-doped porous graphene (NHG);
2) Synthesis of composite catalyst: NHG and potassium chloroplatinate are fed according to the mass ratio of 1:0.05; and (3) dispersing 100mg of NHG in 20mL of deionized water in an ultrasonic manner to prepare an aqueous dispersion of NHG with the concentration of 5mg/mL, then adding 5.0mg of potassium chloroplatinate into the dispersion in an ice bath (0 ℃) temperature environment, stirring in a dark place for reaction for 3 hours, filtering, and freeze-drying to obtain the Pt1/NHG composite catalyst.
Example 3
The preparation method of the Co-single-atom-loaded nitrogen-doped porous graphene composite catalyst (Co 1/NHG) comprises the following steps:
1) Synthesis of nitrogen doped porous graphene (NHG): feeding graphene oxide, hydrogen peroxide and ammonia according to a mass ratio of 1:0.05:30; taking 60mL of graphene oxide aqueous solution with the concentration of 3mg/mL, filling the graphene oxide aqueous solution into a 100mL polytetrafluoroethylene reaction kettle liner, adding 3mL of hydrogen peroxide solution with the mass fraction of 0.3% and 18mL of ammonia water solution with the mass fraction of 28% into the mixture, uniformly mixing, filling the obtained mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction in an oven at 180 ℃ for 8 hours to obtain nitrogen-doped porous graphene (NHG);
2) Synthesis of composite catalyst: charging NHG and cobalt nitrate hexahydrate according to the mass ratio of 1:0.09; and (3) dispersing 50mg of NHG in 50mL of deionized water in an ultrasonic manner to prepare an aqueous dispersion of NHG with the concentration of 1mg/mL, then adding 4.5mg of cobalt nitrate hexahydrate into the aqueous dispersion in an ice bath (0 ℃) temperature environment, stirring and reacting for 3 hours in a dark place, filtering, and freeze-drying to obtain the Co1/NHG composite catalyst.
Example 4
The preparation method of the Fe single-atom-loaded nitrogen-doped porous graphene composite catalyst (Fe 1/NHG) comprises the following steps:
1) Synthesis of nitrogen doped porous graphene (NHG): feeding graphene oxide, hydrogen peroxide and ammonia according to a mass ratio of 1:0.12:24; taking 42mL of graphene oxide aqueous solution with the concentration of 4.47mg/mL, filling the graphene oxide aqueous solution into a 100mL polytetrafluoroethylene reaction kettle liner, adding 7.35mL of hydrogen peroxide solution with the mass fraction of 0.3% and 15.6mL of ammonia water solution with the mass fraction of 28% into the mixture, uniformly mixing, filling the obtained mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 8 hours in a 180 ℃ oven to obtain nitrogen-doped porous graphene (NHG);
2) Synthesis of composite catalyst: NHG and ferric nitrate nonahydrate are fed according to the mass ratio of 1:0.14; and (3) dispersing 60mg of NHG in 50mL of deionized water in an ultrasonic manner to prepare an NHG aqueous dispersion with the concentration of 1.2mg/mL, then adding 8.4mg of potassium chloropalladate into the aqueous dispersion at the temperature of an ice bath (0 ℃), stirring and reacting for 3 hours in a dark place, and performing suction filtration and freeze-drying to obtain the Fe1/NHG composite catalyst.
Example 5
The preparation method of the Au-single-atom-loaded nitrogen-doped porous graphene composite catalyst (Au 1/NHG) comprises the following steps:
1) Synthesis of nitrogen doped porous graphene (NHG): feeding graphene oxide, hydrogen peroxide and ammonia according to a mass ratio of 1:0.05:30; taking 60mL of graphene oxide aqueous solution with the concentration of 3mg/mL, filling the graphene oxide aqueous solution into a 100mL polytetrafluoroethylene reaction kettle liner, adding 3mL of hydrogen peroxide solution with the mass fraction of 0.3% and 18mL of ammonia water solution with the mass fraction of 28% into the mixture, uniformly mixing, filling the obtained mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction in an oven at 180 ℃ for 8 hours to obtain nitrogen-doped porous graphene (NHG);
2) Synthesis of composite catalyst: NHG and chloroauric acid are fed according to the mass ratio of 1:0.04; and (3) dispersing 50mg of NHG in 50mL of deionized water in an ultrasonic manner to prepare an aqueous dispersion of NHG with the concentration of 1mg/mL, then adding 2.0mg of chloroauric acid into the dispersion in an ice bath (0 ℃) temperature environment, stirring and reacting for 3 hours in a dark place, filtering, and freeze-drying to obtain the Au1/NHG composite catalyst.
Example 6
The preparation method of the Pd single-atom-loaded nitrogen-doped porous graphene composite catalyst (Pd 1/NHG) comprises the following steps:
1) Synthesis of nitrogen doped porous graphene (NHG): feeding graphene oxide, hydrogen peroxide and ammonia according to a mass ratio of 1:0.11:20; taking 42.25mL of graphene oxide water solution with the concentration of 3mg/mL, filling the graphene oxide water solution into a 100mL polytetrafluoroethylene reaction kettle liner, adding 4.7mL of hydrogen peroxide solution with the mass fraction of 0.3% and 8.45mL of ammonia water solution with the mass fraction of 28% into the mixture, uniformly mixing, filling the obtained mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 6 hours in a 180 ℃ oven to obtain nitrogen-doped porous graphene (NHG);
2) Synthesis of composite catalyst: charging NHG and potassium palladium chloride according to the mass ratio of 1:0.06; and (3) dispersing 70mg of NHG in 35mL of deionized water in an ultrasonic manner to prepare an aqueous dispersion of NHG with the concentration of 2mg/mL, then adding 4.2mg of potassium chloropalladate into the aqueous dispersion in a cooling bath (10 ℃) temperature environment, stirring in a dark place for reaction for 1h, and carrying out suction filtration and freeze-drying to obtain the Pd1/NHG composite catalyst.
Application example
The Pd1/NHG composite catalyst obtained in the example 1 is applied to the efficient catalytic reduction reaction of aromatic nitro compoundsThe method comprises the following steps: 3ml of a yellow aqueous solution formed by 4-nitrophenol (20 mM) and sodium borohydride (1M) serving as a reducing agent was provided, 1.0mg of the Pd1/NHG composite catalyst obtained in example 1 was added to the above mixed solution, and the reaction was stirred to obtain a reduced product of colorless 4-aminophenol after 10 seconds, which was confirmed by ultraviolet spectroscopic analysis (see FIG. 6) and TOF (switching frequency) = 1915.2min -1 The method comprises the steps of carrying out a first treatment on the surface of the This performance is superior to the relevant catalysts reported so far, as detailed in Table 2.
TABLE 2
References cited in table 2:
[1]J.B.Xi,H.Y.Sun,D.Wang,Z.Y.Zhang,X.M.Duan,J.W.Xiao,F.Xiao,L.M.Liu,S.Wang,Confined-interface-directed synthesis of Palladium single-atom catalysts on graphene/amorphous carbon.Appl.Catal.B-Environ.225(2018),291–297.
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the above examples are presented for clarity of illustration only and are not limiting of the embodiments. Other variations and modifications of the above description will be apparent to those of ordinary skill in the art, and it is not necessary or exhaustive of all embodiments, and thus all obvious variations or modifications that come within the scope of the invention are desired to be protected.
Claims (8)
1. The preparation method of the metal-monoatomic-supported nitrogen-doped porous graphene composite catalyst is characterized by comprising the following steps of:
1) Synthesis of nitrogen doped porous graphene: adding a hydrogen peroxide solution and a nitrogen source into the graphene oxide aqueous solution, uniformly mixing, heating to perform hydrothermal reaction, and obtaining nitrogen-doped porous graphene;
2) Synthesis of monoatomic catalyst: uniformly dispersing the obtained nitrogen-doped porous graphene in water, then adding a metal salt solution into the obtained dispersion liquid, and stirring for reaction in a dark place to obtain the metal-monoatomic-loaded nitrogen-doped porous graphene composite catalyst;
the mass ratio of graphene oxide to hydrogen peroxide to ammonia is 1:0.05:0.05;
the mass ratio of the nitrogen doped porous graphene to the metal salt in the step 2) is 100 (0.3-14);
in the catalytic reduction reaction of the p-nitrophenol, the catalytic efficiency is 1915.2min -1 。
2. The method of claim 1, wherein the concentration of the graphene oxide aqueous solution is 1-10mg/mL; the concentration of the hydrogen peroxide solution is 0.2-30wt.%.
3. The method of claim 1, wherein the nitrogen source is aqueous ammonia.
4. The method according to claim 1, wherein the hydrothermal reaction temperature is 100-220 ℃ for 5-24 hours.
5. The method of claim 1, wherein the concentration of nitrogen-doped porous graphene in the dispersion in step 2) is 0.5-5mg/mL.
6. The preparation method according to claim 1, wherein the metal salt is one or more of water-soluble salts of palladium, cobalt, gold, platinum and iron.
7. The preparation method according to claim 1, wherein the light-shielding stirring reaction temperature is 0-10 ℃ and the time is more than 1 h.
8. The metal monatomic supported nitrogen doped porous graphene composite catalyst prepared by the preparation method of any one of claims 1-7.
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