CN115043400A - Nitrogen-doped hierarchical pore carbon nanoflower material taking ZnO/coal pitch as raw material, and preparation method and application thereof - Google Patents
Nitrogen-doped hierarchical pore carbon nanoflower material taking ZnO/coal pitch as raw material, and preparation method and application thereof Download PDFInfo
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- 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
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Abstract
The invention discloses a nitrogen-doped hierarchical pore carbon nanoflower material taking ZnO/coal pitch as a raw material, a preparation method and application thereof. 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 taking ZnO/coal pitch as a raw material, and a preparation method and application thereof.
Background
With the increase of world energy utilization, especially the rapid increase of global fossil energy usage, the emission of CO from fuel combustion is caused 2 The amount is increasing day by day. CO in the atmosphere as the most predominant greenhouse gas 2 The increasing content of the active ingredients has serious influence on the ecological environment, brings a series of global environmental problems, such as global warming, glacier thawing, sea level rising, seawater acidity increasing, climate abnormality and the like, and seriously threatens the survival and development of human beings. The proposition of the strategic goals of "carbon peaking, carbon neutralization" helps to further demonstrate and interpret the global climate change crisis caused by carbon emissions. 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 appropriate effective method can be adopted to realize CO 2 Trapping, separating and making reasonable use of this is expected to be the most promising and promising strategy for achieving the strategic goals of carbon neutralization. Thus, CO 2 The concept of capture and sequestration utilization of (a) has received considerable attention and research from people.
The porous carbon material has become the current CO by virtue of the advantages of high specific surface area, developed pores, stable structure, abundant surface chemistry, high chemical stability and the like 2 A research hotspot material in the field of trapping and separation. To satisfy CO 2 The efficient capture and separation of the porous carbon adsorbent material requires precise regulation and control of the microstructure and composition of the porous carbon adsorbent material, and the nano customization and accurate cutting of the micro-scale of the pore structure are realized. Currently, to design highly efficient porous carbonaceous CO 2 The adsorbent material is prepared by the following effective methods: (1) the accurate cutting of the pore structure and the accurate regulation and control of the composition proportion of the pore structure of the material mainly focus on the optimized regulation and control of the proportion of micropores and mesopores; (2) carbon surface function integration and surface CO increase 2 Active sites of adsorption, thereby improving CO sequestration by carbonaceous materials 2 The adsorption capacity of (1). Therefore, the method designs high-efficiency porous carbon CO by establishing a controllable preparation technology of the porous carbon material and realizing the nanometer customization and functional integration of the porous carbon material based on the structural design and the surface functional integration of the porous carbon material and the innovation of a synthetic method 2 Capture agentThe difficulty and challenge of research.
Disclosure of Invention
The invention aims to provide a nitrogen-doped hierarchical pore carbon nanoflower material taking ZnO/coal 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 and an in-situ activator precursor, the series effect of ZnO template-in-situ activation is utilized to prepare and synthesize the multistage pore carbon nanoflower with surface nitrogen self-doping, 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 purpose, the invention adopts the following specific technical scheme:
a preparation method of a nitrogen-doped hierarchical pore carbon nanoflower material taking ZnO/coal pitch as a raw material is characterized by comprising the following steps:
s1, ultrasonically and uniformly dissolving coal tar pitch into tetrahydrofuran, and marking as a solution A; stirring and dispersing the ZnO nanoflower material in tetrahydrofuran, and marking as a solution B; then adding the solution A into the solution B under the stirring state, and stirring and mixing for 4.5-5.5 h; 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 ℃ in a protective atmosphere, preserving heat for 2-2.5 hours, naturally cooling to room temperature, taking out a product, and placing the product into 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, soaking the product in dilute hydrochloric acid for reaction for 1.5-2.5 hours, filtering, washing the solid with high-purity water to be neutral, and drying at 65-75 ℃ to obtain the hierarchical porous carbon nanoflower material.
Further, the mass ratio of the coal tar pitch to the ZnO nanoflower material is 1 (4-8); the coal tar pitch concentration 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, the ark is placed in a tube furnace in S2 and S3, Ar gas is introduced, the flow rate of the Ar gas is 50 mL/min, and the ark is heated to 500 +/-50 ℃ or 800 +/-100 ℃ at the heating rate of 5 ℃/min.
Furthermore, the concentration of dilute hydrochloric acid in S2 and S3 is 1-2 mol/L.
Further, 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, adding NaOH solution in the stirring process, continuously reacting for 1.5-2.5 h under a stirring state, then 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 pitch as a raw material.
The nitrogen-doped hierarchical porous carbon nanoflower material taking ZnO/coal pitch as the raw material is used as CO 2 The application of the adsorbent.
The invention takes industrial waste coal pitch as a carbon source and ZnO as a template agent to copy a three-dimensional nanoflower structure, and simultaneously converts the ZnO template agent into an activator ZnCl in situ 2 And in-situ chemical activation pore-forming is carried out, so that a rich pore structure is generated. The hierarchical pore carbon nanoflower material prepared by the method has an outstanding pore structure, the pore size is accurate and controllable, and the nitrogen self-doping amount is high.
Compared with the prior art, the invention has the following technical effects:
(1) the preparation method is simple in preparation process, high in operability and outstanding in economic benefit, and has the potential of large-scale industrial production;
(2) the invention adopts a novel template-in-situ activation tandem treatment method, does not need to add any activating agent, realizes the 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 hierarchical porous carbon nanoflower designed by the invention has an accurate and controllable pore structure and surface nitrogen self-doping function integration, and is beneficial to improving the material qualityCO 2 And (4) adsorption performance.
Drawings
FIG. 1 shows ZnO nanoflower, intermediate transition state product of reaction and HPCNF-xAn XRD pattern of the material;
FIG. 2 is HPCNF-xRaman spectra of the material;
FIG. 3 is HPCNF-xXPS spectra of the material;
FIG. 4 is HPCNF-xPore structure analysis of the material;
FIG. 5 is a scanning electron microscope image of a ZnO nanoflower material;
FIG. 6 is HPCNF-xScanning electron micrographs of the material (a) HPCNF-4, (b) HPCNF-5, (c) HPCNF-6, and (d) HPCNF-8;
FIG. 7 shows HPCNF-xThe material was CO at 0 deg.C (a) and 25 deg.C (b) 2 And (4) an adsorption performance graph.
Detailed Description
Technical objects, technical solutions and effects of the present invention will be further described in order to make the technical objects, technical solutions and effects of the present invention clearer, but the examples are intended to explain the present invention and should not be construed as limiting the present invention, and those who do not specify a specific technique or condition in the examples are performed according to the techniques or conditions described in the literature in the art or according to the product specification.
Example 1
A preparation method of nitrogen-doped hierarchical pore carbon nanoflower material with ZnO/coal pitch as raw material comprises the following steps:
(1) preparing a ZnO nanoflower material: the ZnO nano flower material is prepared by adopting a coprecipitation method, 0.74 g (2.5 mmol) of zinc nitrate hexahydrate and 1.76 g (6.8 mmol) of sodium citrate are accurately weighed and dissolved in 50 mL of H 2 And O, stirring for 30 min at room temperature to completely dissolve and fully mix uniformly, slowly adding 10 mL of NaOH solution with the molar concentration of 1.25 mol/L in the stirring process, continuously reacting for 2 h under the stirring state, centrifuging (6000 r/min, 10 min) to obtain precipitate powder, repeatedly washing the obtained precipitate with high-purity water to neutrality, and drying the obtained powder in an oven at 80 ℃ overnight to obtain the ZnO nanoflower material.
(2) Of multi-stage porous carbon nanoflowersPreparation: firstly, weighing 0.1 g of asphalt (the softening point is 75 ℃), uniformly dissolving the asphalt in 20 mL of tetrahydrofuran solvent by ultrasonic (the power is 200W), and marking as a solution A; ZnO powder of a fixed mass (0.4 g, 0.5 g, 0.6 g, 0.8 g in this order) prepared by the above method was uniformly dispersed in 40 mL of tetrahydrofuran under stirring, and dispersed for 20 min under mechanical stirring (500 r/min), and the solution was designated as solution B. Then, the solution A is slowly added into the solution B under the stirring state, and the two solutions are mixed by stirring for 5 hours to be fully and uniformly mixed. Subsequently, the homogeneously mixed solution was transferred to an oven at 60 ℃ until the solvent was completely evaporated to obtain a powder material. Putting the obtained powder material into a corundum square boat, putting the square boat into a tube furnace, introducing high-purity Ar gas (the purity is 99.99%), introducing 50 mL/min of gas flow, heating to 500 ℃ at the heating rate of 5 ℃/min, preserving heat for 2 h, naturally cooling to room temperature, taking out a product, and putting the product into 20 mL of 2 mol/L dilute hydrochloric acid for soaking reaction for 2 h; then placing in a 60 ℃ oven until the solvent is completely evaporated to dryness to obtain an intermediate transition state pre-carbonized powder material (soaking in hydrochloric acid for reaction to react ZnO with hydrochloric acid to generate ZnCl in situ 2 As an in-situ activator, after soaking, the solvent is volatilized in situ). Putting the obtained powder material into a corundum square boat, putting the square boat into a tube furnace, introducing high-purity Ar gas, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving heat for 2 h, naturally cooling to room temperature, taking out a product, soaking the product in 20 mL of 2 mol/L dilute hydrochloric acid for 2 h, filtering, washing the solid with high-purity water to be neutral, and drying in a 70 ℃ oven for about 10 h to obtain the multi-level porous carbon nano flower marked as HPCNF-x（xAs a ZnO/bitumen mass ratio).
FIG. 1 shows ZnO nanoflower, intermediate transition state product of reaction and HPCNF-xXRD analysis of the material. As shown in FIG. 1 (a), ZnO (PDF # 36-1451) in a hexagonal crystal form was successfully obtained by a coprecipitation method. To demonstrate the reaction mechanism and the in situ activation mechanism, (b) in fig. 1 is XRD analysis of the intermediate product in the preparation reaction process. In the figure 1, (b) is an XRD pattern of a product obtained by mixing ZnO and asphalt (the mass ratio is 5: 1) and then carrying out pre-carbonization treatment at 500 ℃, clearly shows a hexagonal phase ZnO structure, and proves that the pre-carbonizationIn the process, the pitch precursor and ZnO do not have chemical reaction, and the crystal structure of the material can not be damaged. In (b) of FIG. 1, the XRD pattern of the intermediate transition state material obtained by immersing the product after 500 ℃ pre-carbonization treatment in 2M hydrochloric acid and evaporating the dry solvent is shown as (2), ZnCl 2 The existence of the crystal structure indicates that the ZnO hard template agent is dissolved by hydrochloric acid to form ZnCl 2 Crystalline phase with these in situ generated ZnCl 2 The pre-carbonized carbon layer will be etched as a chemical activator to form a rich pore structure. In figure 1, (3) in (b) is XRD pattern of product after 500 deg.C pre-carbonized product acid soaking and product after further 800 deg.C carbonization, and existence of hexagonal phase ZnO indicates activation process, in-situ ZnCl 2 The crystalline phase reacts with reducing C and is converted into ZnO crystalline phase. Such results further demonstrate ZnCl 2 And (3) in-situ activating a pore-forming mechanism. FIG. 1 (c) shows HPCNF-xXRD pattern of (a). All HPCNF- x Material 2 theta = 26 ° And 43 ° There are humps with low diffraction intensity and wide range 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 is HPCNF-xThe Raman spectrogram of the material is mainly used for further characterizing and analyzing the carbon skeleton structure and the graphitization degree of the material. As can be seen from FIG. 2, all HPCNF-xThe material is 1340 cm and 1580 cm respectively -1 Two Raman peaks corresponding to D peak and having double resonance or disordered sp of defect position in material 2 The hybrid carbon structure; the latter corresponds to the G peak, originating from sp 3 The hybridized ordered graphitic carbon atoms vibrate in the lattice plane. The intensity of the D peak is much higher than the intensity of the G peak, indicating a relatively low degree of graphitization of the material.
FIG. 3 is HPCNF-xXPS spectral analysis of the material. The main objective of XPS analysis was to evaluate HPCNF-xThe composition and relative content of elements on the surface of the material. As shown in a of FIG. 3, all HPCNF-xThe material contains three elements of C, N and O. All HPCNF-xThe valence states of the C, N and O elements on the surface of the material are consistent, and the content change of the C, N and O elements is not obviously changed along with the increase of the proportion of the activating agent.
FIG. 4 is HPCNF-xPore structure analysis of materials. In FIG. 4 a is HPCNF-xMaterial N 2 Adsorption and desorption isotherm diagrams. Obviously, as the amount of ZnO is increased, the material has different pore structures. At a relative pressure P/P 0 <Low pressure region of 0.01, with rapidly rising N 2 The adsorption capacity shows that the material has rich micropore pore structures; at the same time, the sample is at a relative pressure P/P 0 >In the 0.8 high-pressure region, there is a rapid rise in N 2 The adsorption capacity indicates that the material has a certain amount of slit-shaped mesoporous and even macroporous pore structures, and the shape of the adsorption isotherm indicates that the material has a hierarchical pore structure of micropores, mesopores and macropores. B and c in FIG. 4 are HPCNF-xThe pore size distribution diagram of the material can clearly find the pore structure of the material with the sizes of micropores (0.5 nm-1.2 nm), mesopores (3 nm-50 nm) and macropores (50 nm-70 nm) in a multi-level pore size. Meanwhile, the prepared HPCNF-4, HPCNF-5, HPCNF-6 and HPCNF-8 materials respectively have high specific surface areas of 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 ZnO nano flower material. As shown in the figure, the prepared ZnO material presents a clear three-dimensional nanoflower morphology structure, the overall particle size is relatively uniform, and the particle size of the nanoflower is 1.5 mu m.
FIG. 6 is HPCNF-xScanning electron micrographs of the material. As shown, all HPCNF-xThe material basically copies the nanometer flower structure of the ZnO template, and the in-situ activation pore-forming process can not damage the appearance structure of the material. However, as the amount of ZnO was increased, slight collapse and deformation of the three-dimensional nanoflower structure occurred, which results should be attributed to the results of the transition in-situ chemical activation causing the collapse of the partial nanosheets.
FIG. 7 shows HPCNF-xMaterial CO 2 Adsorption performance test chart (pretreatment condition: 200 ℃, 8 h; test by using American MacaASAP 2020HD88 physical chemical adsorption apparatus). In FIG. 7 a is HPCNF-xThe adsorption performance of the material at the temperature of 0 ℃ is tested, and the result shows that HThe PCNF-4, HPCNF-5, HPCNF-6 and HPCNF-8 materials had 2.77, 3.57, 3.39 and 3.42 mmol g, respectively, at a pressure of 1 bar -1 CO of 2 And (4) adsorption capacity. In FIG. 7 b is HPCNF-xThe results of the adsorption performance test chart of the material at the temperature of 25 ℃ show that the HPCNF-4, HPCNF-5, HPCNF-6 and HPCNF-8 materials respectively have 2.05, 2.58, 2.26 and 2.41 mmol g at the pressure of 1 bar -1 CO of 2 The amount of adsorption. Analysis and comparison can be carried out, and the HPCNF-5 material has optimal CO 2 The adsorption performance, such results are due to its superior hierarchical pore structure, in particular its high micropore porosity and suitable micropore pore size (see b in fig. 6).
Finally, the relevant parameters for constructing the porous carbon nanoflower material can be adjusted within the response range, and the obvious ZnO/coal pitch mass ratio, carbonization temperature, carbonization time and the like can be correspondingly replaced or adjusted. The above embodiments are merely intended to illustrate the technical solution of the present invention and not to limit the same, 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 (8)
1. A preparation method of a nitrogen-doped hierarchical pore carbon nanoflower material taking ZnO/coal pitch as a raw material is characterized by comprising the following steps:
s1, ultrasonically and uniformly dissolving coal tar pitch into tetrahydrofuran, and marking as a solution A; stirring and dispersing the ZnO nanoflower material in tetrahydrofuran, and marking as a solution B; then adding the solution A into the solution B under the stirring state, and stirring and mixing for 4.5-5.5 h; 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 ℃ in a protective atmosphere, preserving heat for 2-2.5 hours, naturally cooling to room temperature, taking out a product, and placing the product into 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, soaking the product in dilute hydrochloric acid for reaction for 1.5-2.5 hours, filtering, washing the solid with high-purity water to be neutral, and drying at 65-75 ℃ to obtain the hierarchical porous carbon nanoflower material.
2. The preparation method of the nitrogen-doped hierarchical pore carbon nanoflower material taking ZnO/coal pitch as the raw material according to claim 1, wherein the mass ratio of the coal pitch to the ZnO nanoflower material is 1 (4-8); the coal tar pitch concentration 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 nitrogen-doped hierarchical porous carbon nanoflower material with ZnO/coal pitch as raw material according to claim 1,
s2 and S3, the ark is placed in a tube furnace, Ar gas is introduced, the flow rate of the Ar gas is 50 mL/min, and the ark is heated to 500 +/-50 ℃ or 800 +/-100 ℃ at the heating rate of 5 ℃/min.
4. The method for preparing the nitrogen-doped hierarchical porous carbon nanoflower material by using the ZnO/coal pitch as the raw material according to claim 1, wherein the concentration of dilute hydrochloric acid in S2 and S3 is 1-2 mol/L.
5. The method for preparing nitrogen-doped hierarchical pore carbon nanoflower material with ZnO/coal pitch as raw material according to claim 1,
preparing a ZnO nanoflower material: accurately weighing zinc nitrate and sodium citrate to dissolve in H 2 And (3) stirring at room temperature to completely dissolve and uniformly mix the materials, adding a NaOH solution in the stirring process, continuously reacting for 1.5-2.5 h under a 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 nano flower material.
6. The preparation method of the nitrogen-doped hierarchical pore carbon nanoflower material with ZnO/coal pitch as the raw material according to claim 5, wherein the molar ratio of zinc nitrate to sodium citrate to sodium hydroxide is 1 (2.70-2.75) to 5, and the concentration of NaOH solution is 1.25 mol/L.
7. The nitrogen-doped hierarchical porous carbon nanoflower material prepared by the method of any one of claims 1 to 6 and taking ZnO/coal pitch as a raw material.
8. The nitrogen-doped hierarchical porous carbon nanoflower material prepared from ZnO/coal pitch as claimed in claim 7 as CO 2 The application of the adsorbent.
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| 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 |
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| 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 |
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