CN115043400B - Nitrogen-doped hierarchical pore carbon nanoflower material with ZnO/coal tar pitch as raw material, and preparation method and application thereof - Google Patents
Nitrogen-doped hierarchical pore carbon nanoflower material with ZnO/coal tar pitch as raw material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN115043400B CN115043400B CN202210537127.1A CN202210537127A CN115043400B CN 115043400 B CN115043400 B CN 115043400B CN 202210537127 A CN202210537127 A CN 202210537127A CN 115043400 B CN115043400 B CN 115043400B
- Authority
- CN
- China
- Prior art keywords
- zno
- nanoflower
- solution
- coal tar
- tar pitch
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 96
- 239000002057 nanoflower Substances 0.000 title claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- 239000011294 coal tar pitch Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002994 raw material Substances 0.000 title claims abstract description 13
- 239000002149 hierarchical pore Substances 0.000 title claims description 16
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003463 adsorbent Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000011300 coal pitch Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 25
- 238000011065 in-situ storage Methods 0.000 abstract description 16
- 239000003575 carbonaceous material Substances 0.000 abstract description 9
- 230000004913 activation Effects 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000012190 activator Substances 0.000 abstract description 5
- 239000002440 industrial waste Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000011295 pitch Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001994 activation Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000010426 asphalt Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000009656 pre-carbonization Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
-
- 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
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention discloses a nitrogen-doped hierarchical carbon nanoflower material with ZnO/coal tar pitch as a raw material, a preparation method and application thereof, wherein industrial waste pitch is used as a carbon source, znO is used as a template agent and an in-situ activator precursor, the serial efficacy of ZnO template-in-situ activation is utilized to prepare the synthesized surface nitrogen-doped hierarchical carbon nanoflower, and meanwhile, the accurate regulation and control of the pore structure of the carbon nanoflower material are realized by regulating the concentration of ZnO. The porous carbon material prepared by the method can be used as CO 2 An adsorbent.
Description
Technical Field
The invention belongs to the technical field of porous carbon materials, and particularly relates to a nitrogen-doped hierarchical porous carbon nanoflower material with ZnO/coal tar pitch as a raw material, a preparation method and application thereof.
Background
With the world's increased energy utilization, particularly the rapid increase in worldwide fossil energy usage, has led to the combustion of fuel-emitted CO 2 The amount is increasing. As the most dominant greenhouse gas, CO in the atmosphere 2 The increasing content has caused serious influence on the ecological environment, brings a series of global environmental problems, such as global warming, glacier melting, sea level rising, seawater acidity increasing, climate abnormality and the like, and seriously threatens the survival and development of human beings. The "peak carbon, carbon neutralization" strategic targets are presented to help further reveal and interpret carbon emissions causing global climate change crisis. In addition, CO 2 Is also an important industrial raw material, and has a plurality of applications in the fields of inorganic chemical industry, organic chemical industry and the like. If a proper and effective method can be adopted to realize the CO 2 Capturing, separating and reasonably utilizing it is expected to be the most promising and promising strategy for achieving the strategic goals of carbon neutralization. Thus, CO 2 The concept of capturing and sealing utilization is focused on and studied by people.
The porous carbon material has become the current CO by virtue of the advantages of high specific surface area, developed pores, stable structure, rich surface chemistry, high chemical stability and the like 2 The field of trapping and separation is to collect research hot spot materials. To meet CO 2 The high-efficiency capturing and separating of the porous carbon adsorbent material requires accurate regulation and control of the microstructure and composition of the porous carbon adsorbent material, and nano customization and accurate cutting of the microstructure microscale of the porous carbon adsorbent material are realized. Currently, in order to design highly efficient porous carbon CO 2 The effective methods commonly used for the adsorbent materials mainly comprise: (1) Accurate tailoring of pore structures and accurate regulation of composition proportion of pore structures of materials are mainly focused on optimization regulation of micropore and mesoporous proportion; (2) Carbon surface function integration, surface CO increase 2 Active sites of adsorption, thereby improving the carbon material to CO 2 Is used for the adsorption capacity of the catalyst. Therefore, the porous carbon material structure design and surface function integration are surrounded, the innovation of the synthesis method is based, the controllable preparation technology of the porous carbon material is established, the nano customization and function integration of the porous carbon material are realized, and the efficient porous carbon CO is designed 2 Difficulties and challenges in the investigation of capture agents.
Disclosure of Invention
The invention aims to provide a nitrogen-doped hierarchical pore carbon nanoflower material with ZnO/coal tar pitch as a raw material, and a preparation method and application thereof. The porous carbon nanoflower material with the gradient pore structure and the adjustable pore size is prepared by a simple, green and low-cost synthesis process, industrial waste asphalt is used as a carbon source, znO is used as a template agent and an in-situ activator precursor, the serial efficacy of ZnO template-in-situ activation is utilized to prepare the synthetic surface nitrogen self-doped multi-level pore carbon nanoflower, and meanwhile, the pore structure of the carbon nanoflower material is accurately regulated and controlled by regulating and controlling the concentration of ZnO. The porous carbon material prepared by the method can be used as CO 2 An adsorbent.
In order to achieve the above purpose, the invention adopts the following specific technical scheme:
the preparation method of the nitrogen-doped hierarchical pore carbon nanoflower material with ZnO/coal tar pitch as the raw material is characterized by comprising the following steps of:
s1, uniformly dissolving coal tar pitch in tetrahydrofuran by ultrasonic waves, and marking the solution as a solution A; stirring and dispersing ZnO nanoflower material into tetrahydrofuran, and marking as solution B; then adding the solution A into the solution B in a stirring state, and stirring and mixing for 4.5-5.5 hours; then, completely evaporating the mixed solution solvent at 60-65 ℃ to obtain a powder material;
s2, heating the powder material obtained in the step S1 to 500+/-50 ℃ under a protective atmosphere, preserving heat for 2-2.5 hours, naturally cooling to room temperature, taking out a product, and placing the product in dilute hydrochloric acid for soaking reaction for 1.5-2.5 hours; then, completely evaporating the solvent at 60-65 ℃ to obtain a powder material;
s3, heating the powder material obtained in the step S2 to 800+/-100 ℃ under a protective atmosphere, preserving heat for 2-2.5 hours, naturally cooling to room temperature, placing the product into dilute hydrochloric acid for soaking reaction for 1.5-2.5 hours, filtering, washing the solid to be neutral by high-purity water, and drying at 65-75 ℃ to obtain the hierarchical pore carbon nanoflower material.
Further, the mass ratio of the coal tar pitch to the ZnO nanoflower material is 1 (4-8); the concentration of coal tar pitch in the solution A is 0.005 g/mL, and the volume ratio of the solution A to the solution B is 1:2.
Further, in S2 and S3, the ark is placed in a tube furnace, ar gas is introduced, the Ar gas flow is 50mL/min, and the ark is heated to 500+/-50 ℃ or 800+/-100 ℃ at the heating rate of 5 ℃/min.
Further, the concentration of the dilute hydrochloric acid in the S2 and the S3 is 1 mol/L-2 mol/L.
Further, the preparation of the ZnO nanoflower material: accurately weighing zinc nitrate and sodium citrate to dissolve in H 2 In O, stirring at room temperature to completely dissolve and uniformly mix, continuously reacting with NaOH solution added in the stirring process for 1.5-2.5 h under the stirring state, centrifuging to obtain precipitate powder, repeatedly washing the obtained precipitate with high-purity water to be neutral, and drying the obtained powder to obtain the ZnO nanoflower material;
the nitrogen-doped hierarchical pore carbon nanoflower material prepared by the method takes ZnO/coal tar pitch as a raw material.
The ZnO/coal pitch is used asRaw material nitrogen-doped hierarchical pore carbon nanoflower material used as CO 2 Application of adsorbent.
The invention uses industrial waste coal pitch as a carbon source, znO as a template agent to replicate a three-dimensional nano flower structure, and simultaneously converts the ZnO template agent into an activating agent ZnCl in situ 2 Pore formation is carried out through in-situ chemical activation, so that rich pore structures are generated. The hierarchical pore carbon nanoflower material prepared by the method has a superior pore structure, the pore size is accurate and controllable, and the hierarchical pore carbon nanoflower material has high nitrogen self-doping amount.
Compared with the prior art, the invention has the following technical effects:
(1) The preparation process is simple, high in operability and remarkable in economic benefit, and has potential of large-scale industrial production;
(2) The invention adopts a novel template-in-situ activation serial treatment method, does not need to add any activating agent, realizes synchronous regulation and control of the morphology structure and the pore structure, and has the advantages of high efficiency, rapidness and energy conservation;
(3) The multistage pore carbon nanoflower designed by the invention has accurate and controllable pore structure and surface nitrogen self-doping function integration, and is beneficial to improving the CO of the material 2 Adsorption performance.
Drawings
FIG. 1 is a ZnO nanoflower, intermediate transition state reaction product and HPCNF-xXRD pattern of the material;
FIG. 2 shows HPCNF-xRaman spectrogram of the material;
FIG. 3 shows HPCNF-xXPS spectrum diagram of material;
FIG. 4 shows HPCNF-xA pore structure analysis chart of the material;
FIG. 5 is a scanning electron microscope image of ZnO nanoflower material;
FIG. 6 is HPCNF-xScanning electron microscope pictures of materials, (a) HPCNF-4, (b) HPCNF-5, (c) HPCNF-6, and (d) HPCNF-8;
FIG. 7 is a schematic illustration of HPCNF-xThe material was CO at 0 ℃ (a) and 25 ℃ (b) temperature 2 Adsorption performance diagram.
Detailed Description
Further description of the technical solution of the present invention will be made for the purpose of making the technical objects, technical solutions and implementation effects of the present invention more clear, but the examples are intended to explain the present invention and should not be construed as limiting the present invention, and specific techniques or conditions are not noted in the examples, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications.
Example 1
The preparation process of the nitrogen doped hierarchical pore carbon nanoflower material with ZnO/coal tar pitch as material includes the following steps:
(1) Preparing ZnO nanoflower materials: preparation of ZnO nanoflower Material by Co-precipitation, accurate weighing of 0.74 g (2.5 mmol) Zinc nitrate hexahydrate and 1.76 g (6.8 mmol) sodium citrate in 50mL H 2 And (3) in O, stirring at room temperature for 30 min to completely dissolve and fully and uniformly mix, slowly adding 10 mL NaOH solution with the molar concentration of 1.25 mol/L in the stirring process, continuing to react for 2 h in the stirring state, centrifuging (6000 r/min,10 min) to obtain precipitate powder, repeatedly flushing the obtained precipitate with high-purity water to neutrality, and placing the obtained powder in an oven at 80 ℃ to dry overnight to obtain the ZnO nanoflower material.
(2) Preparing hierarchical pore carbon nanoflower: firstly, weighing 0.1 g asphalt (softening point is 75 ℃), and uniformly dissolving the asphalt into 20 mL tetrahydrofuran solvent by ultrasonic waves (power is 200W), and marking the solution as solution A; the ZnO powder prepared by the method was uniformly dispersed in tetrahydrofuran of 40 mL with a fixed mass (0.4 g, 0.5 g, 0.6 g, 0.8 g in this order) under stirring, and was mechanically stirred (500 r/min) for 20 min to be referred to as solution B. Then, the solution a was slowly added to the solution B with stirring, and the two solutions were thoroughly mixed with stirring and mixing 5 h. Subsequently, the uniformly mixed solution was transferred to a 60 ℃ oven until the solvent was completely evaporated to obtain a powder material. Placing the obtained powder material into corundum ark, placing the ark into a tube furnace, introducing high-purity Ar gas (purity is 99.99%), heating to 500 deg.C at 5 deg.C/min at air flow rate of 50mL/min, maintaining the temperature of 2 h, naturally cooling to room temperature, taking out the product, and placing in 2 mol/L thin solution of 20 mLSoaking in hydrochloric acid for reaction 2 h; then, the mixture is placed in a 60 ℃ oven until the solvent is completely evaporated to dryness to obtain the intermediate transition state pre-carbonized powder material (soaking reaction in hydrochloric acid to enable ZnO and hydrochloric acid to react and generate ZnCl in situ) 2 As an in-situ activator, the solvent is volatilized in situ after soaking). Placing the obtained powder material into corundum ark, placing the ark into a tubular furnace, introducing high-purity Ar gas, heating to 800 ℃ at a heating rate of 5 ℃/min with air flow rate of 50mL/min, preserving heat for 2 h, naturally cooling to room temperature, taking out the product, placing the product into 2 mol/L dilute hydrochloric acid of 20 mL for soaking reaction for 2 hours, filtering, washing the solid to neutrality with high-purity water, drying in an oven at 70 ℃ for about 10 h, and obtaining the hierarchical pore carbon nanoflowers, namely HPCNF-x（xThe mass ratio of ZnO/asphalt).
FIG. 1 is a ZnO nanoflower, intermediate transition state reaction product and HPCNF-xXRD analysis of the material. As can be seen from FIG. 1 (a), hexagonal crystalline form of ZnO (PDF # 36-1451) was successfully obtained by the coprecipitation method. To demonstrate the reaction scheme and in situ activation mechanism, (b) in fig. 1 is an XRD analysis for the preparation of the intermediate product of the reaction process. In fig. 1 (b), the XRD pattern of the product obtained by pre-carbonizing ZnO and asphalt (mass ratio 5:1) at 500 ℃ clearly shows the structure of the hexagonal crystalline ZnO, which proves that the asphalt precursor and ZnO do not react chemically during pre-carbonization, and the crystal structure of the material itself is not destroyed. In FIG. 1 (b), XRD patterns of intermediate transition state materials obtained by immersing the product obtained after the pre-carbonization treatment at 500 ℃ in 2M hydrochloric acid to evaporate the dry solvent are shown as ZnCl 2 The existence of the crystal structure indicates that the ZnO hard template is dissolved by hydrochloric acid to form ZnCl 2 Crystalline phases, with these in situ formed ZnCl 2 The pre-carbonized carbon layer will be etched as a chemical activator, forming a rich pore structure. In FIG. 1 (b), XRD patterns of the product obtained after the pre-carbonized product (3) is immersed in acid at 500 ℃ and carbonized at 800 ℃ are shown, and the presence of ZnO in hexagonal phase indicates the occurrence of activation process, in-situ ZnCl 2 The crystal phase reacts with the reducing C and is converted into ZnO crystal phase. Such results further demonstrate that ZnCl 2 In situ activation pore-forming mechanism. In FIG. 1 (c) is HPCNF-xIs a XRD pattern of (C). All HPCNF-xMaterial at 2θ=26 ° And 43 ° Humps with low and wide diffraction intensity exist at the positions corresponding to the (002) and (100) crystal face diffraction peaks of the carbon material respectively, indicating that all HPCNF-xThe material has an amorphous carbon skeleton structure.
FIG. 2 shows HPCNF-xThe Raman spectrum diagram of the material is mainly used for further characterizing and analyzing the carbon skeleton structure of the material and the graphitization degree of the carbon skeleton structure. As can be seen from FIG. 2, all HPCNF-xThe materials are 1340 and 1580 cm respectively -1 There are two Raman peaks, the former corresponding to the D peak, with double resonance or disordered sp of defect sites in the material 2 Hybrid carbon structure induced; the latter corresponds to the G peak and is derived from sp 3 The hybridized ordered graphite carbon atom lattice vibrates in plane. The intensity of the D peak is much higher than the G peak intensity, indicating a relatively low degree of graphitization of the material.
FIG. 3 shows HPCNF-xXPS spectrum analysis graph of material. The main purpose of XPS analysis is to evaluate HPCNF-xThe composition and relative content of the surface elements of the material. As shown in FIG. 3 a, all HPCNF-xThe material contains three elements of C, N and O. From FIGS. 3 b-d, it is evident that all HPCNF-xThe valence states of C, N and O elements on the surface of the material are consistent, and the content change of the C, N and O elements does not have obvious change along with the increase of the proportion of the activator.
FIG. 4 shows HPCNF-xPore structure analysis diagram of material. FIG. 4A shows HPCNF-xMaterial N 2 Adsorption and desorption isotherm plot. Obviously, as the amount of ZnO increases, the material has different pore structures. At relative pressure P/P 0 <0.01 low pressure zone with rapidly rising N 2 Adsorption quantity shows that the material has rich micropore pore structure; at the same time, the sample is at relative pressure P/P 0 >0.8 high voltage region with rapidly rising N 2 Adsorption quantity indicates that a certain amount of slit-shaped mesopores and even macropores exist in the material, and the shape of the adsorption isotherm indicates that micropores, mesopores and macropores of the material exist in a multistage pore structure. In FIG. 4, b and c are HPCNF-xThe pore size distribution diagram of the material can clearly find the pore structure of the material with multi-level pore sizes of micropores (0.5 nm-1.2 nm), mesopores (3 nm-50 nm) and macropores (50 nm-70 nm). At the same timeThe prepared HPCNF-4, HPCNF-5, HPCNF-6 and HPCNF-8 materials respectively have high specific surface areas of 440.3 and 440.3 m 2 g -1 、529.7 m 2 g -1 、737.9 m 2 g -1 And 795.6 m 2 g -1 。
Fig. 5 is a scanning electron microscope image of the ZnO nanoflower material. As shown in the figure, the prepared ZnO material has a clear three-dimensional nano flower morphology structure, the overall particle size is relatively uniform, and the particle size of the nano flower is 1-5 mu m.
FIG. 6 is HPCNF-xScanning electron microscope image of the material. As shown, all HPCNF-xThe material basically replicates the nano flower structure of the ZnO template, which indicates that the in-situ activation pore-forming process does not damage the morphology structure of the material. However, with increasing amounts of ZnO, slight collapse and deformation of the three-dimensional nanoflower structure occurs, and such results should be attributed to the results of the transition in situ chemical activation resulting in collapse of the local nanoplatelets.
FIG. 7 is a schematic illustration of HPCNF-xMaterial CO 2 Adsorption performance test chart (pretreatment conditions: 200 ℃,8 h; using a U.S. mike ASAP2020HD88 physico-chemical adsorption instrument). FIG. 7A shows HPCNF-xThe adsorption performance test chart of the material at the temperature of 0 ℃ shows that HPCNF-4, HPCNF-5, HPCNF-6 and HPCNF-8 materials respectively have 2.77,3.57,3.39 and 3.42 mmol g under the pressure of 1 bar -1 CO of (c) 2 Adsorption amount. FIG. 7 b shows HPCNF-xThe adsorption property test chart of the material at 25 ℃ shows that HPCNF-4, HPCNF-5, HPCNF-6 and HPCNF-8 materials respectively have 2.05,2.58,2.26 and 2.41 mmol g under the pressure of 1 bar -1 CO of (c) 2 Adsorption amount. Analysis and comparison show that the HPCNF-5 material has optimal CO 2 Adsorption properties, such results benefit from their superior multi-stage pore structure, particularly their high micropore porosity and suitable micropore size (as seen in fig. 6 b).
Finally, in the invention, the relevant parameters of the porous carbon nanoflower material construction can be adjusted in the response range, and the obvious ZnO/coal pitch mass ratio, carbonization temperature, carbonization time and the like can be replaced or adjusted correspondingly. The foregoing embodiments are merely illustrative of the technical aspects of the present invention and are not limiting, and although the present invention has been described with reference to preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (5)
1. The preparation method of the nitrogen-doped hierarchical pore carbon nanoflower material with ZnO/coal tar pitch as the raw material is characterized by comprising the following steps of:
s1, uniformly dissolving coal tar pitch in tetrahydrofuran by ultrasonic waves, and marking the solution as a solution A; stirring and dispersing ZnO nanoflower material into tetrahydrofuran, and marking as solution B; then adding the solution A into the solution B in a stirring state, and stirring and mixing 4.5-h-5.5-h; then, completely evaporating the mixed solution solvent at 60-65 ℃ to obtain a powder material, wherein the mass ratio of coal pitch to ZnO nanoflower material is 1 (4-8);
s2, heating the powder material obtained in the step S1 to 500+/-50 ℃ under a protective atmosphere, preserving heat for 2-2.5 hours, naturally cooling to room temperature, taking out a product, and placing the product in dilute hydrochloric acid for soaking reaction for 1.5-2.5 hours; then, completely evaporating the solvent at 60-65 ℃ to obtain a powder material;
s3, heating the powder material obtained in the step S2 to 800+/-100 ℃ under a protective atmosphere, preserving heat for 2-2.5 hours, naturally cooling to room temperature, placing the product into dilute hydrochloric acid for soaking reaction for 1.5-2.5 hours, filtering, washing the solid to be neutral by high-purity water, and drying at 65-75 ℃ to obtain the hierarchical pore carbon nanoflower material;
the concentration of the dilute hydrochloric acid in S2 and S3 is 1 mol/L-2 mol/L;
preparing ZnO nanoflower materials: accurately weighing zinc nitrate and sodium citrate to dissolve in H 2 In O, stirring at room temperature to completely dissolve and uniformly mix, continuously reacting with NaOH solution added in the stirring process for 1.5-2.5 h under the stirring state, centrifuging to obtain precipitate powder, repeatedly washing the obtained precipitate with high-purity water to neutrality, and drying the obtained powder to obtain ZnO nanoflower material, wherein the mol of zinc nitrate, sodium citrate and sodium hydroxide are calculated as the mol of ZnO nanoflower materialThe ratio is 1 (2.70-2.75), 5, and the concentration of NaOH solution is 1.25 mol/L.
2. The method for preparing the nitrogen-doped hierarchical pore carbon nanoflower material by using ZnO/coal tar pitch as a raw material, according to claim 1, wherein the concentration of the coal tar pitch in the solution A is 0.005 g/mL, and the volume ratio of the solution A to the solution B is 1:2.
3. The method for preparing the nitrogen-doped hierarchical porous carbon nanoflower material with ZnO/coal tar pitch as a raw material, according to claim 1, wherein in S2 and S3, a square boat is placed in a tube furnace, ar gas is introduced, the Ar gas flow rate is 50mL/min, and the material is heated to 500+/-50 ℃ or 800+/-100 ℃ at a heating rate of 5 ℃/min.
4. A nitrogen-doped hierarchical pore carbon nanoflower material prepared by the method of any one of claims 1 to 3 and using ZnO/coal tar pitch as a raw material.
5. The nitrogen-doped hierarchical porous carbon nanoflower material with ZnO/coal tar pitch as a raw material of claim 4 as CO 2 Application of adsorbent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210537127.1A CN115043400B (en) | 2022-05-18 | 2022-05-18 | Nitrogen-doped hierarchical pore carbon nanoflower material with ZnO/coal tar pitch as raw material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210537127.1A CN115043400B (en) | 2022-05-18 | 2022-05-18 | Nitrogen-doped hierarchical pore carbon nanoflower material with ZnO/coal tar pitch as raw material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115043400A CN115043400A (en) | 2022-09-13 |
| CN115043400B true CN115043400B (en) | 2024-01-12 |
Family
ID=83159138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210537127.1A Active CN115043400B (en) | 2022-05-18 | 2022-05-18 | Nitrogen-doped hierarchical pore carbon nanoflower material with ZnO/coal tar pitch as raw material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115043400B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288070A (en) * | 2013-04-02 | 2013-09-11 | 大连理工大学 | Method for preparing nitrogen-doped porous carbon from heavy organic component in coal liquefaction residue |
| CN108455582A (en) * | 2018-04-17 | 2018-08-28 | 福州大学 | A kind of preparation method of the three-dimensional porous grapheme material of low cost |
| CN110451509A (en) * | 2019-08-20 | 2019-11-15 | 江西省科学院应用化学研究所 | A method of nitrogen-doped porous carbon material is prepared by activator of zinc nitrate |
| CN113149003A (en) * | 2020-11-12 | 2021-07-23 | 同济大学 | In-situ ultra-small zinc nanocrystalline template method for synthesizing nitrogen-doped porous carbon, method and application |
| CN114316790A (en) * | 2021-12-31 | 2022-04-12 | 江南大学 | Preparation method of hydrangeal-shaped nano zinc oxide-doped heat-conducting polyurethane coating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018014659A1 (en) * | 2016-07-22 | 2018-01-25 | 中国石油化工股份有限公司 | Carbon-based porous material, preparation method therefor and use thereof |
-
2022
- 2022-05-18 CN CN202210537127.1A patent/CN115043400B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288070A (en) * | 2013-04-02 | 2013-09-11 | 大连理工大学 | Method for preparing nitrogen-doped porous carbon from heavy organic component in coal liquefaction residue |
| CN108455582A (en) * | 2018-04-17 | 2018-08-28 | 福州大学 | A kind of preparation method of the three-dimensional porous grapheme material of low cost |
| CN110451509A (en) * | 2019-08-20 | 2019-11-15 | 江西省科学院应用化学研究所 | A method of nitrogen-doped porous carbon material is prepared by activator of zinc nitrate |
| CN113149003A (en) * | 2020-11-12 | 2021-07-23 | 同济大学 | In-situ ultra-small zinc nanocrystalline template method for synthesizing nitrogen-doped porous carbon, method and application |
| CN114316790A (en) * | 2021-12-31 | 2022-04-12 | 江南大学 | Preparation method of hydrangeal-shaped nano zinc oxide-doped heat-conducting polyurethane coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115043400A (en) | 2022-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107459029B (en) | Nitrogen/metal atom doped hollow polyhedral nano carbon shell material and preparation method thereof | |
| Zhang et al. | Morphology-controlled fabrication of Co3O4 nanostructures and their comparative catalytic activity for oxygen evolution reaction | |
| CN111876160B (en) | Carbon aerogel material, preparation method thereof and application of carbon aerogel material as heavy metal contaminated soil remediation material | |
| CN111333127B (en) | Hierarchical porous honeycomb nickel oxide microsphere and preparation method thereof | |
| Asgarian et al. | The effect of different sources of porous carbon on the synthesis of nanostructured boron carbide by magnesiothermic reduction | |
| Wang et al. | Large surface area porous carbon materials synthesized by direct carbonization of banana peel and citrate salts for use as high-performance supercapacitors | |
| CN103193630B (en) | LNNU-1 serial nanometer MOF (Metal Organic Framework) type porous material and preparation method thereof | |
| Ling et al. | Synthesis of mesoporous MgO nanoplate by an easy solvothermal–annealing method | |
| CN107837816B (en) | Fe2O3/g-C3N4Composite system, preparation method and application | |
| Li et al. | ZnO nanosheet/squeezebox-like porous carbon composites synthesized by in situ pyrolysis of a mixed-ligand metal–organic framework | |
| Wang et al. | Molten shell-activated, high-performance, un-doped Li4SiO4 for high-temperature CO2 capture at low CO2 concentrations | |
| Singh et al. | Pure and strontium carbonate nanoparticles functionalized microporous carbons with high specific surface areas derived from chitosan for CO 2 adsorption | |
| Zhao et al. | Synthesis of precursor-derived 1D to 2D Co 3 O 4 nanostructures and their pseudo capacitance behaviour | |
| CN115818638A (en) | Nitrogen-sulfur-doped hierarchical porous carbon and preparation method thereof | |
| Jia et al. | Preparation and characterization of porous HMO/PAN composite adsorbent and its adsorption–desorption properties in brine | |
| Naik et al. | Facile synthesis of fibrous, mesoporous Ni 1− x O nanosponge supported on Ni foam for enhanced pseudocapacitor applications | |
| Siddiqa et al. | A spongy Rhizophora mucronata derived ultra-high surface area activated carbon for high charge density supercapacitor device | |
| Liu et al. | Mesoporous carbon–ZrO 2 composites prepared using thermolysis of zirconium based metal–organic frameworks and their adsorption properties | |
| CN115043400B (en) | Nitrogen-doped hierarchical pore carbon nanoflower material with ZnO/coal tar pitch as raw material, and preparation method and application thereof | |
| Liao et al. | Template-free hydrothermal synthesis of 3D hierarchical Co3O4 microflowers constructed by mesoporous nanoneedles | |
| Liu et al. | Sustainable catalytic graphitization of biomass to graphitic porous carbon by constructing permeation network with organic ligands | |
| Liang et al. | Synthesis and catalysis properties of NiO flower-like spheres and nanosheets: Water-induced phase transformation of nickel hydroxides | |
| Xu et al. | Preparation, modification and adsorption properties of spinel-type H1. 6Mn1. 6O4 lithium-ion sieves with spiny nanotube morphology | |
| Li et al. | Self-assembled Mg5 (CO3) 4 (OH) 2· 4H2O nanosheet as an effective catalyst in the Baeyer–Villiger oxidation of cyclohexanone | |
| Liang et al. | A universal strategy towards porous carbons with ultrahigh specific surface area for high-performance symmetric supercapacitor applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |