CN117339554A - Porous carbon sphere, preparation method and application thereof - Google Patents
Porous carbon sphere, preparation method and application thereof Download PDFInfo
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- CN117339554A CN117339554A CN202210733211.0A CN202210733211A CN117339554A CN 117339554 A CN117339554 A CN 117339554A CN 202210733211 A CN202210733211 A CN 202210733211A CN 117339554 A CN117339554 A CN 117339554A
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000008188 pellet Substances 0.000 claims abstract description 65
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 238000001179 sorption measurement Methods 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 238000010000 carbonizing Methods 0.000 claims abstract description 27
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000004793 Polystyrene Substances 0.000 claims abstract description 23
- 229920002223 polystyrene Polymers 0.000 claims abstract description 23
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000005530 etching Methods 0.000 claims abstract description 13
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 150000002940 palladium Chemical class 0.000 claims abstract description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000011049 filling Methods 0.000 claims abstract description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 30
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000000274 adsorptive effect Effects 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012508 resin bead Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 39
- 238000001035 drying Methods 0.000 description 21
- 238000001914 filtration Methods 0.000 description 21
- 238000005406 washing Methods 0.000 description 21
- 235000019441 ethanol Nutrition 0.000 description 16
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 15
- 238000001354 calcination Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 238000010907 mechanical stirring Methods 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000011324 bead Substances 0.000 description 8
- 239000012798 spherical particle Substances 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
Abstract
The application discloses a porous carbon sphere, a preparation method and application thereof, wherein the method comprises the following steps: mixing raw materials containing aromatic amine and resin monomer, and carrying out polymerization reaction to obtain a composite precursor; adding palladium salt into the composite precursor for adsorption to obtain palladium-loaded resin pellets; filling a solution containing a pore-forming agent into the palladium-loaded resin pellets, stirring, carbonizing and etching to obtain the porous carbon pellets; the aromatic amine is at least one selected from aniline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine and triphenylamine; the resin monomer is chloromethylated polystyrene spheres. The preparation method has simple process, self-assembly at room temperature, introduction of carbon source, and one-step nitrogen doping of nitrogen source to synthesize the product. The pore structure inside the carbon sphere can be regulated by changing the dosage of the pore-forming agent, and the catalyst has wide application prospect in the fields of catalysis and adsorption separation.
Description
Technical Field
The application relates to a porous carbon ball, a preparation method and application thereof, and belongs to the technical field of porous carbon material preparation.
Background
The carbon material has the characteristics of rich pore channel structure, large specific surface area, strong adsorptivity, large adsorption capacity and the like. At present, the chemical industry of China rapidly develops, and the carbon material has the characteristics, is low in price and environment-friendly, so that the carbon material is widely applied to various fields of adsorption, separation, catalysis and the like. The porous carbon ball has the advantages of smooth surface, controllable pore structure, adjustable pore diameter, small fluid resistance and the like, and is mainly divided into: wood activated carbon, coal activated carbon, fruit shell activated carbon, coconut shell activated carbon, and the like. The porous carbon sphere prepared by taking the polystyrene crosslinking microsphere as the raw material accords with the low-carbon environment-friendly development direction, and has wide prospect. On the basis of taking the palladium as a carrier, a certain amount of metal palladium is loaded, and the catalyst also has good application effect in the field of catalysis. The existing porous carbon sphere prepared by taking aromatic amine-polystyrene resin as a raw material has more micropore structures, which is unfavorable for mass transfer process of molecules in the porous carbon sphere in adsorption and catalysis processes.
Disclosure of Invention
The invention aims to provide a method for preparing a porous carbon sphere, which has simple process and can finish the preparation process of nitrogen doping and porous carbon sphere by a one-step method. The addition of the metal palladium can play roles of improving the active surface and inhibiting side reactions, thereby achieving the effect of increasing the reaction activity. The purpose of adjusting the internal pore structure of the carbon sphere can be achieved by adjusting the dosage of the pore-forming agent, and the method has wide application prospect in the fields of catalysis and adsorption separation.
According to one aspect of the present application, there is provided a method of preparing a porous carbon sphere, the method comprising the steps of:
(1) Mixing raw materials containing aromatic amine and resin monomer, and carrying out polymerization reaction to obtain a composite precursor;
(2) Adding palladium salt into the composite precursor for adsorption to obtain palladium-loaded resin pellets;
(3) Filling a solution containing a pore-forming agent into the palladium-loaded resin pellets, stirring, carbonizing and etching to obtain the porous carbon pellets;
the aromatic amine is at least one selected from aniline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine and triphenylamine;
the resin monomer is chloromethylated polystyrene spheres.
Optionally, in the step (1), the polymerization reaction conditions are: the reaction temperature is 20-120 ℃ and the reaction time is 0.5-8 hours.
Optionally, in the step (1), the polymerization reaction conditions are: the reaction temperature is 50-90 ℃ and the reaction time is 1-6 hours.
Alternatively, the reaction temperature is selected from any value of 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or any value between any two points.
Alternatively, the reaction time is selected from any of 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, or any value between any two of the foregoing.
Optionally, in the step (3), the mass ratio of the pore-forming agent to the palladium-loaded resin pellets is 1-5: 1.
optionally, in the step (3), the pore-forming agent is at least one selected from ethyl orthosilicate and methyl orthosilicate.
Optionally, in the step (3), the solvent in the solution is a mixed solution of water and ethanol, and the volume ratio of water to ethanol is 0.2-4: 1.
alternatively, the upper limit of the volume ratio of water to ethanol is selected from 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, and the lower limit is selected from 0.2, 0.4, 0.6, 0.8, 1.0, 1.2.
Optionally, the volume ratio of the pore-forming agent to the mixed solution is 0.1-1.0: 1.
optionally, the volume ratio of the pore-forming agent to the mixed solution is the upper limit selected from 0.6, 0.7, 0.8, 0.9 and 1.0; the lower limit is selected from 0.1, 0.2, 0.3, 0.4, 0.5.
Optionally, in the step (1), the mass ratio of the aromatic amine to the resin monomer is 0.1-10: 1.
optionally, in the step (1), the mass ratio of the aromatic amine to the resin monomer is 0.5-1.0: 1.
optionally, the mass ratio of the aromatic amine to the resin monomer is selected from any value of 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0 or any value between any two points.
Optionally, in the step (2), the mass ratio of the palladium acetate to the composite precursor is 0.001-0.2: 1.
optionally, the upper limit of the mass ratio of the palladium acetate to the composite precursor is selected from 0.14, 0.15, 0.16, 0.17, 0.18, 0.19 and 0.20; the lower limit is selected from 0.001, 0.002, 0.003, 0.004, 0.005, 0.006.
Optionally, in the step (2), the conditions of the adsorption are: the adsorption temperature is 10-60 ℃ and the adsorption time is 2-24 hours.
Alternatively, the adsorption temperature is selected from any value of 10 ℃, 15 ℃,20 ℃,25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ or any value between any two points.
Alternatively, the adsorption time is selected from any value of 2 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, or any value between any two points.
Optionally, in the step (3), the stirring condition is: the stirring temperature is 10-90 ℃, and the stirring time is 4-24 hours.
Optionally, the upper limit of the stirring temperature is selected from 10 ℃, 15 ℃,20 ℃,25 ℃, 30 ℃; the lower limit is selected from 70 ℃, 75 ℃, 80 ℃, 85 ℃ and 90 ℃.
Optionally, the upper limit of the stirring time is selected from 20 hours, 21 hours, 22 hours, 23 hours and 24 hours; the lower limit is selected from 4 hours, 5 hours, 6 hours, 7 hours, 8 hours.
Optionally, in the step (3), the carbonization condition is: the carbonization temperature is 300-1000 ℃ and the carbonization time is 2-12 hours.
Optionally, the upper limit of carbonization temperature is selected from 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ and 1000 ℃; the lower limit is 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ and 600 ℃.
Optionally, the upper limit of carbonization time is selected from 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours; the lower limit is selected from 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours.
Optionally, the carbonization atmosphere is an inert gas, and the inert gas is at least one selected from nitrogen, argon and helium.
Optionally, in the step (3), the etching conditions are: the etching agent is hydrofluoric acid, the etching temperature is 10-90 ℃, and the etching time is 2-24 hours.
Optionally, the upper limit of the etching temperature is selected from 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃; the lower limit is selected from 10deg.C, 15deg.C, 20deg.C, 25deg.C, 30deg.C, 35deg.C, and 40deg.C.
Optionally, the etching time is selected from 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours; the lower limit is selected from 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours.
According to another aspect of the present application, there is provided a porous carbon sphere prepared by the method, the porous carbon sphere having a specific surface area of 30 to 1500m 2 /g; the load of palladium in the porous carbon sphere is 0.01-5%.
According to yet another aspect of the present application, there is also provided the use of porous carbon spheres in catalytic and/or adsorptive separation.
The beneficial effects that this application can produce include:
according to the method, aromatic amine and chloromethylated polystyrene balls are adopted to be polycondensed as precursors, a carbon source and a nitrogen source are introduced, then a carrier metal palladium and a pore-forming agent are added through a one-step method, so that a palladium-loaded nitrogen-doped composite ball is obtained, and the composite ball is carbonized and etched to obtain the metal palladium-loaded nitrogen-doped porous carbon ball. The preparation method has simple process, nitrogen doping and palladium loading are carried out in one step, the two functions of improving the surface activity of the porous carbon sphere, and the size of the pore structure inside the carbon sphere can be regulated by adjusting the dosage of the pore-forming agent. The catalyst is mixed and stirred at room temperature, so that the energy consumption is saved, the environment is protected, complicated procedures in the traditional catalyst preparation process are greatly reduced, the economic and environmental benefits are remarkable, and the catalyst has a wide application prospect in the fields of catalysis and adsorption separation.
Drawings
FIG. 1 is an external view of the precursor resin obtained in examples 1 and 2 of the present invention.
FIG. 2 is an external view of porous carbon spheres obtained in examples 4, 5, 6 and 8 of the present invention.
FIG. 3 is a BET plot of porous carbon spheres obtained in example 2 of the present invention.
FIG. 4 is a BET plot of porous carbon spheres obtained in example 3 of the present invention.
FIG. 5 is a BET plot of porous carbon spheres obtained in example 7 of the present invention.
FIG. 6 is a BET plot of porous carbon spheres obtained in examples 9 and 10 of the present invention.
FIG. 7 is a graph showing pore size distribution of porous carbon spheres obtained in example 9 of the present invention.
FIG. 8 shows SEM images of porous carbon spheres obtained in examples 7, 9 and 10 of the present invention ((a) SEM image of example 7 at 500nm scale, (b) SEM image of example 7 at 2 μm scale, (c) SEM image of example 9 at 500nm scale, (d) SEM image of example 9 at 2 μm scale, (e) SEM image of example 10 at 500nm scale, and (f) SEM image of example 10 at 2 μm scale).
FIG. 9 is a graph showing the palladium loading in porous carbon spheres obtained in examples 7, 9 and 10 of the present invention.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, the starting materials and reagents in the examples of this application were purchased commercially and used as received.
The measuring instrument employed in the embodiments of the present application is: the specific surface area of the porous carbon spheres was tested on a Kang Da four-station physical adsorption quadrarorb S manufactured by QuantaChrome; the loadings of the porous carbon spheres prepared in examples 7, 9 and 10 were characterized using a Perkinelmer CP-OES 7300DV type ICP-OES. SEM testing porous carbon spheres were characterized using a su8220 instrument.
Comparative example 1
10g of chloromethylated polystyrene spheres, 7.8g of o-phenylenediamine and 50ml of absolute ethanol are soaked for 12 hours, heated to 70 ℃ in a water bath and polymerized for 2 hours under mechanical stirring. The mixture was washed, filtered and dried, and 0.024g of palladium acetate and 20ml of benzene were added to 3.00g of the polymerized resin prepared above, followed by magnetic stirring for 24 hours. Cooling to room temperature, filtering, washing and drying to obtain resin pellets. Adding 15ml of ethanol and water and 2.00g of ethyl orthosilicate into the resin pellets, magnetically stirring for 24 hours at room temperature of 20 ℃, placing the pellets into a tube furnace, heating and carbonizing in a nitrogen atmosphere, and calcining at constant temperature of 600 ℃ for 3 hours to complete carbonizing, thus obtaining the palladium-silicon dioxide-carbon composite pellets. The obtained composite spheres are added with 20ml of hydrofluoric acid, 20ml of absolute ethyl alcohol and 120ml of water, and magnetically stirred for 24 hours at room temperature of 20 ℃ to obtain the nitrogen-doped porous carbon spheres loaded with metal palladium.
Specific surface area measured by physical adsorption of nitrogen 24.011m 2 And/g. The precursor is purple black spherical particles after the polymerization of the o-phenylenediamine and the chloromethylated polystyrene spheres.
Comparative example 2
10g of chloromethylated polystyrene spheres, 7.8g of o-phenylenediamine and 50ml of absolute ethanol are soaked for 12 hours, heated to 70 ℃ in a water bath and polymerized for 2 hours under mechanical stirring. Washing, filtering and drying, adding 0.024g of palladium acetate and 7ml of benzene to 1.00g of polymerized resin prepared above, and magnetically stirring for 24 hours. Cooling to room temperature, filtering, washing and drying to obtain resin pellets. Adding 30ml of ethanol and 6.00g of ethyl orthosilicate into the resin pellets respectively, magnetically stirring for 24 hours at room temperature of 20 ℃, placing the pellets into a tube furnace, heating and carbonizing in a nitrogen atmosphere, and calcining at constant temperature of 600 ℃ for 3 hours to complete carbonizing, thus obtaining the palladium-silicon dioxide-carbon composite pellets. The obtained composite spheres are added with 20ml of hydrofluoric acid, 20ml of absolute ethyl alcohol and 120ml of water, and magnetically stirred for 24 hours at room temperature of 20 ℃ to obtain the nitrogen-doped porous carbon spheres loaded with metal palladium.
Specific surface area measured by physical adsorption of Nitrogen 15.243m 2 And/g. The precursor is purple black spherical particles after the polymerization of the o-phenylenediamine and the chloromethylated polystyrene spheres.
Comparative example 3
10g of chloromethylated polystyrene spheres, 7.8g of o-phenylenediamine and 50ml of absolute ethanol are soaked for 12 hours, heated to 140 ℃ in an oil bath and polymerized for 2 hours under mechanical stirring. The mixture was washed, filtered and dried, and 0.024g of palladium acetate and 20ml of benzene were added to 3.00g of the polymerized resin prepared above, followed by magnetic stirring for 24 hours. Cooling to room temperature, filtering, washing and drying to obtain resin pellets. Adding 15ml of ethanol and water and 3.00g of ethyl orthosilicate into the resin pellets, magnetically stirring for 24 hours at room temperature of 20 ℃, placing the pellets into a tube furnace, heating and carbonizing in a nitrogen atmosphere, and calcining at constant temperature of 600 ℃ for 3 hours to complete carbonizing, thus obtaining the palladium-silicon dioxide-carbon composite pellets. The obtained composite spheres are added with 20ml of hydrofluoric acid, 20ml of absolute ethyl alcohol and 120ml of water, and magnetically stirred for 24 hours at room temperature of 20 ℃ to obtain the nitrogen-doped porous carbon spheres loaded with metal palladium.
Specific surface area 47.476m measured by physical adsorption of Nitrogen 2 And/g. The precursor is carbon black color spherical particles after the polymerization of the o-phenylenediamine and the chloromethylated polystyrene spheres.
Example 1
10g of chloromethylated polystyrene spheres, 7.8g of o-phenylenediamine and 50ml of absolute ethanol are soaked for 12 hours, heated to 70 ℃ in a water bath and polymerized for 2 hours under mechanical stirring. The mixture was washed, filtered and dried, and 0.024g of palladium acetate and 20ml of benzene were added to 3.00g of the polymerized resin prepared above, followed by magnetic stirring for 24 hours. Cooling to room temperature, filtering, washing and drying to obtain resin pellets. Adding 15ml of ethanol and water and 3.00g of ethyl orthosilicate into the resin pellets, magnetically stirring for 24 hours at room temperature of 20 ℃, placing the pellets into a tube furnace, heating and carbonizing in a nitrogen atmosphere, and calcining at constant temperature of 600 ℃ for 3 hours to complete carbonizing, thus obtaining the palladium-silicon dioxide-carbon composite pellets. The obtained composite spheres are added with 20ml of hydrofluoric acid, 20ml of absolute ethyl alcohol and 120ml of water, and magnetically stirred for 24 hours at room temperature of 20 ℃ to obtain the nitrogen-doped porous carbon spheres loaded with metal palladium.
Specific surface area 516.072m measured by physical adsorption of Nitrogen 2 And/g. The precursor is purple black spherical particles after the polymerization of the o-phenylenediamine and the chloromethylated polystyrene spheres, and the precursor is shown in (a) of fig. 1.
Example 2
10g of chloromethylated polystyrene spheres, 7.8g of o-phenylenediamine and 50ml of absolute ethanol are soaked for 12 hours, heated to 70 ℃ in a water bath and polymerized for 2 hours under mechanical stirring. The mixture was washed, filtered and dried, and 0.024g of palladium acetate and 20ml of benzene were added to 2.99g of the polymerized resin prepared above, followed by magnetic stirring for 24 hours. Cooling to room temperature, filtering, washing and drying to obtain resin pellets. Adding 15ml of ethanol and 6.02g of ethyl orthosilicate into the resin pellets respectively, magnetically stirring for 24 hours at room temperature of 20 ℃, placing the pellets into a tube furnace, heating and carbonizing in a nitrogen atmosphere, and calcining at constant temperature of 800 ℃ for 3 hours to complete carbonizing, thus obtaining the palladium-silicon dioxide-carbon composite pellets. The obtained composite spheres are added with 20ml of hydrofluoric acid, 20ml of absolute ethyl alcohol and 120ml of water, and magnetically stirred for 24 hours at room temperature of 20 ℃ to obtain the nitrogen-doped porous carbon spheres loaded with metal palladium.
Specific surface area 38.517m measured by physical adsorption of Nitrogen 2 /g, see FIG. 3.
Example 3
20.25g of chloromethylated polystyrene beads, 13.76g of o-phenylenediamine and 100ml of absolute ethanol are soaked for 12 hours, heated to 60 ℃ in a water bath and polymerized for 2 hours under mechanical stirring. Washing, filtering and drying, adding 0.0065g palladium acetate and 7ml benzene to the 1.00g polymerized resin prepared above, stirring magnetically for 24 hours. Cooling to room temperature, filtering, washing and drying to obtain resin pellets. Adding 15ml of ethanol and water and 1.03g of ethyl orthosilicate into the resin pellets, magnetically stirring for 24 hours at the room temperature of 16 ℃, placing the pellets into a tube furnace, heating and carbonizing in a nitrogen atmosphere, and calcining at the constant temperature of 600 ℃ for 3 hours to complete carbonizing, thereby obtaining the palladium-silicon dioxide-carbon composite pellets. The obtained composite spheres were added with 10ml of hydrofluoric acid, 10ml of absolute ethanol and 60ml of water, and magnetically stirred at room temperature of 20 ℃ for 24 hours, thereby obtaining nitrogen-doped porous carbon spheres loaded with metallic palladium.
The precursors after polymerization of the o-phenylenediamine and chloromethylated polystyrene spheres were dark brown spherical particles, see (b) in fig. 1. Specific surface area 35.426m measured by physical adsorption of Nitrogen 2 /g, see FIG. 4.
Example 4
20.25g of chloromethylated polystyrene beads, 13.76g of o-phenylenediamine and 100ml of absolute ethanol are soaked for 12 hours, heated to 60 ℃ in a water bath and polymerized for 2 hours under mechanical stirring. Washing, filtering and drying, adding 0.0058g palladium acetate and 7ml benzene to the 1.00g polymerized resin prepared above, and magnetically stirring for 24 hours. Cooling to room temperature, filtering, washing and drying to obtain resin pellets. Adding 15ml of ethanol and water and 3.02g of ethyl orthosilicate into the resin pellets respectively, magnetically stirring for 24 hours at the room temperature of 16 ℃, placing the pellets into a tube furnace, heating and carbonizing in a nitrogen atmosphere, and calcining at the constant temperature of 600 ℃ for 3 hours to complete carbonizing, thereby obtaining the palladium-silicon dioxide-carbon composite pellets. The obtained composite spheres were added with 10ml of hydrofluoric acid, 10ml of absolute ethanol and 60ml of water, and magnetically stirred at room temperature of 20 ℃ for 24 hours, thereby obtaining nitrogen-doped porous carbon spheres loaded with metallic palladium.
Specific surface area 156.476m measured by physical adsorption of Nitrogen 2 And/g. The appearance was observed as black spherical particles, see a in fig. 2.
Example 5
20.25g of chloromethylated polystyrene beads, 13.76g of o-phenylenediamine and 100ml of absolute ethanol are soaked for 12 hours, heated to 60 ℃ in a water bath and polymerized for 2 hours under mechanical stirring. Washed, filtered and dried, 0.0071g palladium acetate, 10ml benzene was added to the 0.98g polymerized resin prepared above, and magnetically stirred for 24 hours. Cooling to room temperature, filtering, washing and drying to obtain resin pellets. Adding 10ml of ethanol and 1.00g of ethyl orthosilicate into each resin pellet, adding ammonia water, adjusting pH to 12, magnetically stirring for 24 hours at the room temperature of 18 ℃, placing into a tube furnace, heating and carbonizing in a nitrogen atmosphere, and calcining at the constant temperature of 600 ℃ for 3 hours to complete carbonizing, thereby obtaining the palladium-silicon dioxide-carbon composite pellet. The obtained composite spheres were added with 10ml of hydrofluoric acid, 10ml of absolute ethanol and 60ml of water, and magnetically stirred at room temperature of 20 ℃ for 24 hours, thereby obtaining nitrogen-doped porous carbon spheres loaded with metallic palladium.
Specific surface area 152.136m measured by physical adsorption of Nitrogen 2 And/g. The appearance was observed as black spherical particles, see b in fig. 2.
Example 6
20.25g of chloromethylated polystyrene beads, 13.76g of o-phenylenediamine and 100ml of absolute ethanol are soaked for 12 hours, heated to 60 ℃ in a water bath and polymerized for 2 hours under mechanical stirring. Washing, filtering and drying, adding 0.0097g palladium acetate and 10ml benzene to the prepared 1.00g polymerized resin, and magnetically stirring for 24 hours. Cooling to room temperature, filtering, washing and drying to obtain resin pellets. Adding 25ml of ethanol, 15ml of water and 2.01g of ethyl orthosilicate into the resin pellets, adding ammonia water, adjusting pH to 11, magnetically stirring for 24 hours at room temperature of 20 ℃, placing the pellets into a tube furnace, heating and carbonizing in a nitrogen atmosphere, and calcining at constant temperature of 700 ℃ for 3 hours to complete carbonizing, thereby obtaining the palladium-silicon dioxide-carbon composite pellets. The obtained composite spheres were added with 10ml of hydrofluoric acid, 10ml of absolute ethanol and 60ml of water, and magnetically stirred at room temperature of 20 ℃ for 24 hours, thereby obtaining nitrogen-doped porous carbon spheres loaded with metallic palladium.
Specific surface area 372.023m measured by physical adsorption of Nitrogen 2 And/g. The appearance was observed as black powdery particles, see c in fig. 2.
Example 7
20.25g of chloromethylated polystyrene beads, 13.76g of o-phenylenediamine and 100ml of absolute ethanol are soaked for 12 hours, heated to 60 ℃ in a water bath and polymerized for 2 hours under mechanical stirring. Washing, filtering and drying, adding 0.0097g palladium acetate and 10ml benzene to the prepared 1.00g polymerized resin, and magnetically stirring for 24 hours. Cooling to room temperature, filtering, washing and drying to obtain resin pellets. Adding 10ml of ethanol and 2.07g of ethyl orthosilicate into the resin pellets respectively, adding ammonia water, adjusting the pH to be 11, placing the pellets in a tube furnace after 24 hours at the room temperature of 20 ℃, heating and carbonizing the pellets in a nitrogen atmosphere, and calcining the pellets at the constant temperature of 600 ℃ for 3 hours after programming to obtain the palladium-silicon dioxide-carbon composite pellets. The obtained composite spheres were added with 10ml of hydrofluoric acid, 10ml of absolute ethanol and 60ml of water, and magnetically stirred at room temperature of 20 ℃ for 24 hours, thereby obtaining nitrogen-doped porous carbon spheres loaded with metallic palladium.
Fig. 8 (a) is an SEM image of example 7 at a scale of 5nm, and (b) is an SEM image of example 7 at a scale of 2 μm, thereby confirming synthesis of the target product. Specific surface area 30.429m measured by physical adsorption of Nitrogen 2 /g, see FIG. 5. The palladium loading was characterized by ICP, see fig. 9.
Example 8
20.25g of chloromethylated polystyrene beads, 13.76g of o-phenylenediamine and 100ml of absolute ethanol are soaked for 12 hours, heated to 60 ℃ in a water bath and polymerized for 2 hours under mechanical stirring. Washing, filtering and drying, adding 0.0312g palladium acetate and 25ml benzene to the prepared 2.33g polymerized resin, and magnetically stirring for 24 hours. Cooling to room temperature, filtering, washing and drying to obtain resin pellets. Adding 25ml of ethanol, 20ml of water and 2.33g of ethyl orthosilicate into the resin pellets, adding ammonia water, adjusting the pH to be 11, placing the pellets in a tube furnace after 24 hours at the room temperature of 20 ℃, heating and carbonizing the pellets in a nitrogen atmosphere, and calcining the pellets at the constant temperature of 750 ℃ for 3 hours after programming to obtain the palladium-silicon dioxide-carbon composite pellets. The obtained carbon sphere is added with 20ml of hydrofluoric acid, 20ml of absolute ethyl alcohol and 120ml of water, and magnetically stirred for 24 hours at room temperature of 20 ℃ to obtain the nitrogen-doped porous carbon sphere loaded with metal palladium.
Specific surface area 380.412m measured by physical adsorption of Nitrogen 2 /g. The appearance was observed as black powdery particles, see d in fig. 2.
Example 9
20.25g of chloromethylated polystyrene beads, 13.76g of o-phenylenediamine and 100ml of absolute ethanol are soaked for 12 hours, heated to 60 ℃ in a water bath and polymerized for 2 hours under mechanical stirring. Washing, filtering and drying, adding 0.0067g palladium acetate and 10ml benzene to the 1.02g polymerized resin prepared above, stirring magnetically for 24 hours. Cooling to room temperature, adding ammonia water dropwise, adjusting pH to be 9, filtering, washing and drying to obtain resin pellets. Adding 20ml of ethanol and water and 1.00g of ethyl orthosilicate into the resin pellets, magnetically stirring for 24 hours at the room temperature of 18 ℃, placing the pellets into a tube furnace, heating and carbonizing in a nitrogen atmosphere, and calcining at the constant temperature of 600 ℃ for 3 hours after programming to complete carbonizing, thus obtaining the palladium-silicon dioxide-carbon composite pellets. The obtained composite spheres were added with 10ml of hydrofluoric acid, 10ml of absolute ethanol and 60ml of water, and magnetically stirred at room temperature of 20 ℃ for 24 hours, thereby obtaining nitrogen-doped porous carbon spheres loaded with metallic palladium.
Fig. 8 (c) is an SEM image of example 9 at a scale of 5nm, and (d) is an SEM image of example 9 at a scale of 2 μm, thereby confirming the synthesis of the target product. Specific surface area 373.415m measured by physical adsorption of Nitrogen 2 /g, see FIG. 6. The pore size distribution is mainly micropores, mesopores are mainly micropores, and a part of macropores exist, as shown in fig. 7. The introduction of pore structures of micropores, mesopores and partial macropores in the spherical activated carbon greatly improves the mass transfer process of molecules in the spherical activated carbon. The palladium loading was characterized by ICP, see fig. 9.
Example 10
20.25g of chloromethylated polystyrene beads, 13.76g of o-phenylenediamine and 100ml of absolute ethanol are soaked for 12 hours, heated to 60 ℃ in a water bath and polymerized for 2 hours under mechanical stirring. Washing, filtering and drying, adding 0.0074g palladium acetate and 10ml benzene to the prepared 1.00g polymerized resin, and magnetically stirring for 24 hours. Cooling to room temperature, adding ammonia water dropwise, adjusting pH to be 12, filtering, washing and drying to obtain resin pellets. Adding 10ml of ethanol and water and 1.00g of ethyl orthosilicate into the resin pellets, magnetically stirring for 24 hours at the room temperature of 18 ℃, placing the pellets into a tube furnace, heating and carbonizing in a nitrogen atmosphere, and calcining at the constant temperature of 500 ℃ for 3 hours to complete carbonizing, thereby obtaining the palladium-silicon dioxide-carbon composite pellets. The obtained composite spheres were added with 10ml of hydrofluoric acid, 10ml of absolute ethanol and 60ml of water, and magnetically stirred at room temperature of 20 ℃ for 24 hours, thereby obtaining nitrogen-doped porous carbon spheres loaded with metallic palladium.
FIG. 8 (e) is an SEM image of example 10 at a scale of 5nm, and (f) is an SEM image of example 10 at a scale of 2. Mu.mSEM images, thus demonstrating the synthesis of the target product. Specific surface area 35.734m measured by physical adsorption of Nitrogen 2 And/g, see FIG. 6, is much lower than the results of example 9. The palladium loading was characterized by ICP, see fig. 9.
Example 11 characterization of morphology and Structure of porous carbon spheres
SEM was performed on the porous carbon spheres in examples 1 to 10 using a scanning electron microscope, respectively. As typified by example 7, example 9, and example 10, the results shown in fig. 8 were obtained, and fig. 6 is a BET characterization of the porous carbon spheres obtained in example 9 and example 10; fig. 9 is a chart showing ICP characterization of the porous carbon spheres obtained in examples 7, 9 and 10, and as can be seen from fig. 9, the target product was obtained.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (10)
1. A method for preparing a porous carbon sphere, which is characterized by comprising the following steps:
(1) Mixing raw materials containing aromatic amine and resin monomer, and carrying out polymerization reaction to obtain a composite precursor;
(2) Adding palladium salt into the composite precursor for adsorption to obtain palladium-loaded resin pellets;
(3) Filling a solution containing a pore-forming agent into the palladium-loaded resin pellets, stirring, carbonizing and etching to obtain the porous carbon pellets;
the aromatic amine is at least one selected from aniline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine and triphenylamine;
the resin monomer is chloromethylated polystyrene spheres.
2. The method according to claim 1, wherein in the step (1), the polymerization reaction conditions are: the reaction temperature is 20-120 ℃ and the reaction time is 0.5-8 hours;
preferably, in the step (1), the polymerization reaction conditions are as follows: the reaction temperature is 50-90 ℃ and the reaction time is 1-6 hours.
3. The method according to claim 1, wherein in the step (3), the mass ratio of the pore-forming agent to the palladium-supporting resin beads is 1 to 5:1, a step of;
preferably, in the step (3), the pore-forming agent is at least one selected from ethyl orthosilicate and methyl orthosilicate;
preferably, in the step (3), the solvent in the solution is a mixed solution of water and ethanol, and the volume ratio of the water to the ethanol is 0.2-4: 1, a step of;
preferably, the volume ratio of the pore-forming agent to the mixed solution is 0.1-1.0: 1.
4. the method according to claim 1, wherein in the step (1), the mass ratio of the aromatic amine to the resin monomer is 0.1 to 10:1, a step of;
preferably, in the step (1), the mass ratio of the aromatic amine to the resin monomer is 0.5-1.0: 1.
5. the method according to claim 1, wherein in the step (2), the mass ratio of the palladium salt to the composite precursor is 0.001 to 0.2:1.
6. the method according to claim 1, wherein in the step (2), the conditions of the adsorption are: the adsorption temperature is 10-60 ℃ and the adsorption time is 2-24 hours;
preferably, in the step (3), the stirring condition is: the stirring temperature is 10-90 ℃, and the stirring time is 4-24 hours.
7. The method according to claim 1, wherein in the step (3), the condition for carbonization is: the carbonization temperature is 300-1000 ℃ and the carbonization time is 2-12 hours;
preferably, in the step (3), the carbonized atmosphere is an inert gas, and the inert gas is at least one selected from nitrogen, argon and helium.
8. The method according to claim 1, wherein in the step (3), the etching conditions are: the etching agent is hydrofluoric acid, the etching temperature is 10-90 ℃, and the etching time is 2-24 hours.
9. The porous carbon sphere prepared by the method of any one of claims 1 to 8, wherein the porous carbon sphere has a specific surface area of 30 to 1500m 2 /g；
The load of palladium in the porous carbon sphere is 0.01-5%.
10. Use of at least one of the porous carbon spheres prepared by the preparation method of any one of claims 1 to 8 or the porous carbon spheres of claim 9 in catalytic and/or adsorptive separation.
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