Preparation method of polyfurfuryl alcohol resin derived porous glass carbon microspheres
The preparation method of porous glassy carbon microspheres derived from furan methanol resin solves the problems of low preparation efficiency and poor dispersion of porous glassy carbon microspheres in the existing technology, and realizes efficient and low-cost production of porous glassy carbon microspheres.
Patent Information
- Application Number
- CN202511103859.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-07
- Publication Date
- 2025-10-28
AI Technical Summary
Existing methods for preparing porous glassy carbon microspheres have the disadvantages of high cost, harsh conditions, low preparation efficiency, uneven sphere size and poor dispersion, which affect the specific surface area and pore structure performance.
Porous glassy carbon microspheres were prepared by using furan-methanol as reactants and through polymerization reactions of surfactants and acid catalysts, combined with inerting, aging, drying, pyrolysis and activation steps.
The preparation process is simple, efficient and low-cost. The spheres are uniform in size and well dispersed. The specific surface area can reach 1378m2/g, making it suitable for industrial production.
Smart Images
Figure CN120841491A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of carbon materials and their preparation technology, and in particular to a method for preparing porous glassy carbon microspheres derived from polyfuran methanol resin. Background Technology
[0002] Porous glassy carbon microspheres possess excellent chemical stability, mechanical properties, temperature resistance, and electrical conductivity, along with high specific surface area and strong adsorption capacity. Therefore, porous glassy carbon microspheres have broad potential applications in catalyst supports, gas adsorption and separation, cyclization control, energy batteries, and controlled drug release, attracting significant attention. However, existing methods for preparing carbon spheres suffer from drawbacks such as high cost, stringent conditions, and low efficiency. Furthermore, existing methods produce carbon spheres with non-uniform size and a tendency to agglomerate, resulting in poor dispersibility, low specific surface area, and poor activation, thus affecting the pore structure and performance of the porous carbon spheres. Therefore, improving the preparation process to obtain carbon spheres with uniform size and good dispersibility has become a critical problem urgently needing to be solved in the industry. Summary of the Invention
[0003] To overcome the shortcomings of existing preparation techniques, the technical objective of this invention is to provide a method for preparing polyfuran-methanol resin-derived porous glassy carbon microspheres. The obtained derived porous glassy carbon microspheres have uniform size and good dispersibility, with a specific surface area reaching 1378 m². 2 / g.
[0004] The preparation method of the polyfuran-methanol resin-derived porous glassy carbon microspheres of the present invention includes: Step (1) uses furanol as a reactant and causes it to undergo a polymerization reaction under the action of surfactant and acid catalyst; Step (2) The polymerization product is inertized using an inertizing agent; Step (3) Wash the inerted product until neutral, and after aging and drying, obtain polyfuran methanol resin microspheres; Step (4) involves pyrolyzing the polyfuran-methanol resin microspheres to obtain glassy carbon microspheres; Step (5) activate the glassy carbon microspheres to obtain porous glassy carbon microspheres.
[0005] Preferably, in step (1), the acid catalyst includes inorganic acid and organic acid; preferably, the mass ratio of acid catalyst to furan-methanol is (0.1-3):1; more preferably, the acid catalyst is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, lactic acid, and oxalic acid.
[0006] Preferably, in step (1), the surfactant is poloxamer; more preferably, the mass ratio of the surfactant to furanol is (0.1-3):1.
[0007] Preferably, in step (1), the polymerization reaction temperature is 60-90℃ and the polymerization reaction time is 1-5h.
[0008] Preferably, in step (2), the inerting agent is 1-10 mol / L sulfuric acid; more preferably, the mass ratio of the inerting agent to furanol is (1-10):1.
[0009] Preferably, in step (2), the inerting temperature is 60–120°C and the inerting time is 0.5–5 h. More preferably, the inerting time is 3–5 h.
[0010] Preferably, in step (3), the aging temperature is room temperature and the aging time is 12 to 36 hours.
[0011] Preferably, in step (3), the drying temperature is 60-95℃ and the drying time is 12-48h.
[0012] Preferably, in step (4), the pyrolysis temperature is 700–1100℃ and the pyrolysis time is 1–5h.
[0013] Preferably, in step (5), the activator is selected from at least one of potassium bicarbonate, sodium bicarbonate, calcium carbonate, nickel chloride or their hydrates; preferably, the mass ratio of the activator to the glassy carbon microspheres is (1-5):1; more preferably, the activation temperature is 700-1100°C and the activation time is 1-5 h. Attached Figure Description
[0014] Figure 1 These are SEM images of the resin spheres and porous glassy carbon microspheres prepared in Example 7; where (left) are resin microspheres and (right) are glassy carbon microspheres. Figure 2 These are TEM images of the porous glass microspheres prepared in Example 7; Figure 3 The XRD pattern of the porous glassy carbon microspheres prepared in Example 7; Figure 4 The nitrogen (77K) adsorption-desorption isotherm of the porous glassy carbon microspheres prepared in Example 7; Figure 5 The image shows a SEM image of the glassy carbon microspheres prepared in Comparative Example 1. Figure 6 This is a SEM image of the glassy carbon microspheres prepared in Comparative Example 2. Detailed Implementation
[0015] The present invention is further illustrated by the following embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the present invention.
[0016] This invention relates to a method for preparing derived porous glassy carbon microspheres using polyfuran-methanol resin spheres. The method uses furan-methanol as a reactant, and polyfuran-methanol resin microspheres are obtained through emulsion polymerization, followed by drying, pyrolysis, and activation to produce porous glassy carbon microspheres.
[0017] Furan-methanol is used as a reactant, and a polymerization reaction is carried out in the presence of a surfactant and an acid catalyst. The surfactant includes, but is not limited to, poloxamer (F127). The mass ratio of surfactant to furan-methanol can be (0.1–3):1. The mass ratio of acid catalyst to furan-methanol can also be (0.1–3):1. The acid catalyst includes inorganic acids and / or organic acids. The acid catalyst includes, but is not limited to, one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, lactic acid, and oxalic acid. The polymerization reaction temperature can be 60–90°C, and the reaction time can be 1–5 h.
[0018] The solvents used in the polymerization reaction include, but are not limited to, deionized water, anhydrous ethanol, or mixtures thereof. For example, the solvent is a mixture of deionized water and anhydrous ethanol at a mass ratio of (0–5):1. As an example, the mass ratio of solvent to furanol is (3–8):1.
[0019] The purpose of inertizing the polymerization product with an inertizing agent is to prevent the resin balls from agglomerating during the drying process. Inertization with sulfuric acid promotes further reaction and cross-linking of the functional groups on the surface of the resin balls, leading to their consumption and a reduction in the number of active groups on the product surface, which improves the product's dispersibility. The inertizing agent can be 1–10 mol / L sulfuric acid. For example, the concentration of sulfuric acid can be 5 mol / L. The mass ratio of sulfuric acid to furanol / methanol can be (1–10):1. The inertization temperature can be 60–120℃ (e.g., 100℃), and the inertization time can be 0.5–5 h.
[0020] After inerting, the product is washed with deionized water until neutral. The resulting product is aged at room temperature and then dried to obtain polyfuran-methanol resin microspheres. The aging time can be 12–36 hours (e.g., 1 day). The drying temperature can be 60–95℃, and the drying time can be 12–48 hours.
[0021] Glassy carbon microspheres are obtained by pyrolysis of polyfuran-methanol resin microspheres. The pyrolysis temperature can be 700–1100℃, and the pyrolysis time can be 1–5 h.
[0022] Porous glassy carbon microspheres are prepared by activating glassy carbon microspheres with an activating agent. The activating agent includes, but is not limited to, at least one of potassium bicarbonate, sodium bicarbonate, calcium carbonate, nickel chloride, or its hydrate (NiCl2·6H2O). The mass ratio of activating agent to glassy carbon microspheres can be (1–5):1. The activation temperature can be 700–1100℃, and the activation time can be 1–5 h.
[0023] In an optional embodiment, a method for preparing derived porous glassy carbon microspheres using polyfuran-methanol resin spheres employs furan-methanol as the raw material, poloxamer (F127) as the surfactant (poloxamer / furan-methanol ratio = 0.1–3 by mass), acid as the catalyst (catalyst / furan-methanol ratio = 0.1–3 by mass), deionized water and anhydrous ethanol as the mixed solvent (deionized water / anhydrous ethanol ratio = 0–5 by mass), and solvent / furan-methanol ratio = 3–8 by mass. The polymerization reaction temperature is 60–90°C, the rotation speed is 100–500 rpm, and the reaction time is 1–5 h. After the reaction is completed, inerting is performed using 5 mol / L sulfuric acid as a dehydration and crosslinking catalyst (sulfuric acid / furan-methanol ratio = 1–10 by mass), the inerting temperature is 100°C, and the inerting time is 0.5–5 h. After the reaction is complete, the reaction product is washed with deionized water until neutral. The resulting resin microspheres are aged at room temperature for 1 day, and then dried at 60–95℃ for 12–48 h to obtain polyfuran-methanol resin microspheres. The resin microspheres are then pyrolyzed into glassy carbon microspheres. The pyrolysis temperature is 700–1100℃, and the pyrolysis time is 1–5 h. The glassy carbon microspheres are then activated to obtain porous glassy carbon microspheres. The activator can be KHCO3, NaHCO3, CaCO3, NiCl2·6H2O, or a mixture thereof. The activator / glassy carbon microspheres ratio is 1–5 by mass. The activation temperature is 700–1100℃, and the pyrolysis time is 1–5 h.
[0024] Compared with the prior art, the present invention has the following advantages:
[0025] (1) The preparation process is simple and efficient, avoiding harsh and complex preparation techniques. The raw materials used, furanol and methanol, are widely available and inexpensive, resulting in low cost. The reaction conditions are mild and the reaction time is short, leading to high preparation efficiency, which is conducive to large-scale production and can meet the requirements of industrial production. (2) The prepared resin spheres and porous glassy carbon microspheres have uniform size and good dispersibility. For example, the glassy carbon microspheres prepared by this invention can achieve a specific surface area of up to 1300 m² after activation. 2 / g or more (e.g., 1378m) 2 / g).
[0026] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values in the examples below.
[0027] Example 1
[0028] The materials were added according to the mass ratio of furanol:poloxamer:deionized water:ethanol:hydrochloric acid = 20g:10g:120g:40g:10g. First, furanol, poloxamer, and ethanol were added sequentially to deionized water, and the mixture was mechanically stirred for 5 minutes at 250 rpm. Then, hydrochloric acid was added, and stirring continued for 10 minutes. The temperature was then gradually increased to 80℃, and the reaction was allowed to proceed for 1 hour. Next, 140g of sulfuric acid (5mol / L concentration) was added to the reaction solution for inerting treatment at 100℃ for 3 hours. After the reaction was complete, the reaction product was washed with deionized water until neutral, aged at room temperature for 1 day, and then dried at 85℃ for 20 hours to obtain polyfuranol resin microspheres. The polyfuranol resin microspheres were then pyrolyzed into glassy carbon microspheres at 800℃ for 1 hour. The glassy carbon microspheres were then activated to prepare porous glassy carbon microspheres. KHCO3 was used as the activator. The mass ratio of activator to glassy carbon microspheres was 3:1. The activation temperature was 800℃, and the activation time was 1 hour.
[0029] Example 2
[0030] Materials were added according to the mass ratio of furanol:poloxamer:deionized water:ethanol:hydrochloric acid = 20g:10g:100g:60g:10g. First, furanol, poloxamer, and ethanol were added sequentially to deionized water, and mechanically stirred for 5 minutes at 250 rpm. Then, hydrochloric acid was added, and stirring continued for 10 minutes. The temperature was then gradually increased to 80℃, and the reaction was allowed to proceed for 1 hour. Next, 140g of sulfuric acid (5mol / L) was added for inerting at 100℃ for 3 hours. After the reaction was complete, the reaction product was washed with deionized water until neutral, aged at room temperature for 1 day, and then dried at 85℃ for 20 hours to obtain polyfuranol resin microspheres. The polyfuranol resin microspheres were then pyrolyzed into glassy carbon microspheres at 800℃ for 1 hour. The glassy carbon microspheres were then activated to prepare porous glassy carbon microspheres. KHCO3 was used as the activator. The mass ratio of activator to glassy carbon microspheres was 3:1. The activation temperature was 800℃, and the activation time was 1 hour.
[0031] Example 3
[0032] Materials were added according to the mass ratio of furanol:poloxamer:deionized water:ethanol:hydrochloric acid = 20g:10g:80g:80g:10g. First, furanol, poloxamer, and ethanol were added sequentially to deionized water, and mechanically stirred for 5 minutes at 250 rpm. Then, hydrochloric acid was added, and stirring continued for 10 minutes. The temperature was then gradually increased to 80℃, and the reaction was allowed to proceed for 1 hour. Next, 140g of sulfuric acid (5mol / L) was added for inerting at 100℃ for 3 hours. After the reaction was complete, the reaction product was washed with deionized water until neutral, aged at room temperature for 1 day, and then dried at 85℃ for 20 hours to obtain polyfuranol resin microspheres. The polyfuranol resin microspheres were then pyrolyzed into glassy carbon microspheres at 800℃ for 1 hour. The glassy carbon microspheres were then activated to prepare porous glassy carbon microspheres. KHCO3 was used as the activator. The mass ratio of activator to glassy carbon microspheres was 3:1. The activation temperature was 800℃, and the activation time was 1 hour.
[0033] Example 4
[0034] Materials were added according to the mass ratio of furanol:poloxamer:deionized water:ethanol:hydrochloric acid = 20g:10g:60g:100g:10g. First, furanol, poloxamer, and ethanol were added sequentially to deionized water, and mechanically stirred for 5 minutes at 250 rpm. Then, hydrochloric acid was added, and stirring continued for 10 minutes. The temperature was then gradually increased to 80℃, and the reaction was allowed to proceed for 1 hour. Next, 140g of sulfuric acid (5mol / L) was added for inerting at 100℃ for 3 hours. After the reaction was complete, the reaction product was washed with deionized water until neutral, aged at room temperature for 1 day, and then dried at 85℃ for 20 hours to obtain polyfuranol resin microspheres. The polyfuranol resin microspheres were then pyrolyzed into glassy carbon microspheres at 800℃ for 1 hour. The glassy carbon microspheres were then activated to prepare porous glassy carbon microspheres. KHCO3 was used as the activator. The mass ratio of activator to glassy carbon microspheres was 3:1. The activation temperature was 800℃, and the activation time was 1 hour.
[0035] Example 5
[0036] Materials were added according to the mass ratio of furanol:poloxamer:deionized water:ethanol:hydrochloric acid = 20g:10g:40g:120g:10g. First, furanol, poloxamer, and ethanol were added sequentially to deionized water, and mechanically stirred for 5 minutes at 250 rpm. Then, hydrochloric acid was added, and stirring continued for 10 minutes. The temperature was then gradually increased to 80℃, and the reaction was allowed to proceed for 1 hour. Next, 140g of sulfuric acid (5mol / L) was added for inerting at 100℃ for 3 hours. After the reaction was complete, the reaction product was washed with deionized water until neutral, aged at room temperature for 1 day, and then dried at 85℃ for 20 hours to obtain polyfuranol resin microspheres. The polyfuranol resin microspheres were then pyrolyzed into glassy carbon microspheres at 800℃ for 1 hour. The glassy carbon microspheres were then activated to prepare porous glassy carbon microspheres. KHCO3 was used as the activator. The mass ratio of activator to glassy carbon microspheres was 3:1. The activation temperature was 800℃, and the activation time was 1 hour.
[0037] Example 6
[0038] Materials were added according to the mass ratio of furanol:poloxamer:deionized water:ethanol:hydrochloric acid = 20g:10g:20g:140g:10g. First, furanol, poloxamer, and ethanol were added sequentially to deionized water, and mechanically stirred for 5 minutes at 250 rpm. Then, hydrochloric acid was added, and stirring continued for 10 minutes. The temperature was then gradually increased to 80℃, and the reaction was allowed to proceed for 1 hour. Next, 140g of sulfuric acid (5mol / L) was added for inerting at 100℃ for 3 hours. After the reaction was complete, the reaction product was washed with deionized water until neutral, aged at room temperature for 1 day, and then dried at 85℃ for 20 hours to obtain polyfuranol resin microspheres. The polyfuranol resin microspheres were then pyrolyzed into glassy carbon microspheres at 800℃ for 1 hour. The glassy carbon microspheres were then activated to prepare porous glassy carbon microspheres. KHCO3 was used as the activator. The mass ratio of activator to glassy carbon microspheres was 3:1. The activation temperature was 800℃, and the activation time was 1 hour.
[0039] Example 7
[0040] Materials were added according to the mass ratio of furanol:poloxamer:deionized water:ethanol:hydrochloric acid = 20g:10g:80g:80g:10g. First, furanol, poloxamer, and ethanol were added sequentially to deionized water, and mechanically stirred for 5 minutes at 250 rpm. Then, hydrochloric acid was added, and stirring continued for 10 minutes. The temperature was then gradually increased to 80℃, and the reaction was allowed to proceed for 1 hour. Next, 120g of sulfuric acid (5mol / L) was added for inerting at 100℃ for 3 hours. After the reaction was complete, the reaction product was washed with deionized water until neutral, aged at room temperature for 1 day, and then dried at 85℃ for 20 hours to obtain polyfuranol resin microspheres. The polyfuranol resin microspheres were then pyrolyzed into glassy carbon microspheres at 800℃ for 1 hour. The glassy carbon microspheres were then activated to prepare porous glassy carbon microspheres. KHCO3 was used as the activator. The mass ratio of activator to glassy carbon microspheres was 3:1. The activation temperature was 800℃, and the activation time was 1 hour.
[0041] The samples prepared in Example 7 were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), XRD, and N2 (77K) isothermal adsorption-desorption experiments.
[0042] The morphology of the resin spheres and glassy carbon microspheres was characterized by scanning electron microscopy, and the results are as follows: Figure 1 As shown. The resin spheres are uniform in size and have good dispersibility, with a diameter of approximately 1.5 micrometers. The glassy carbon microspheres are uniform in size and have good dispersibility, with a diameter of approximately 1 micrometer.
[0043] The morphology of the glassy carbon microspheres was characterized by transmission electron microscopy, and the results are as follows: Figure 2 As shown, the glassy carbon microspheres are uniform in size, well-dispersed, and have a diameter of approximately 1 micrometer.
[0044] The phase structure of the glassy carbon microspheres was characterized by XRD, and the results are as follows: Figure 3 As shown, broadened diffraction peaks appear near 23° and 43°, which are attributed to the (002) and (100) crystal planes of graphite, respectively, making it a typical amorphous carbon material.
[0045] The pore structure of the glassy carbon microspheres was characterized by N2 (77K) isothermal adsorption-desorption experiments, and the results are as follows: Figure 4 As shown in Table 1, the specific surface area of the microspheres was calculated using the Brunauer-Emmett-Teller (BET) method. The specific surface area was 1378 m². 2 / g, pore volume 1cm 3The average pore size of the sample was calculated to be 1.4 nm using nonlocal density functional theory (NLDFT), classifying it as microporous. Furthermore, the adsorption-desorption isotherms exhibited a slight hysteresis loop in the medium-pressure region, indicating the presence of some mesopores in the sample; while significant adsorption was observed in the high-pressure region, indicating the presence of macropores.
[0046] Characterization results show that the resin balls and derived glassy carbon microspheres provided by the present invention have uniform size, good dispersibility, high specific surface area, and hierarchical pores.
[0047] Example 8
[0048] Materials were added according to the mass ratio of furanol:poloxamer:deionized water:ethanol:hydrochloric acid = 20g:10g:80g:80g:10g. First, furanol, poloxamer, and ethanol were added sequentially to deionized water, and mechanically stirred for 5 minutes at 250 rpm. Then, hydrochloric acid was added, and stirring continued for 10 minutes. The temperature was then gradually increased to 80℃, and the reaction was allowed to proceed for 1 hour. Next, 100g of sulfuric acid (5mol / L) was added for inerting at 100℃ for 3 hours. After the reaction was complete, the reaction product was washed with deionized water until neutral, aged at room temperature for 1 day, and then dried at 85℃ for 20 hours to obtain polyfuranol resin microspheres. The polyfuranol resin microspheres were then pyrolyzed into glassy carbon microspheres at 800℃ for 1 hour. The glassy carbon microspheres were then activated to prepare porous glassy carbon microspheres. KHCO3 was used as the activator. The mass ratio of activator to glassy carbon microspheres was 3:1. The activation temperature was 800℃, and the activation time was 1 hour.
[0049] Example 9
[0050] Materials were added according to the mass ratio of furanol:poloxamer:deionized water:ethanol:hydrochloric acid = 20g:10g:80g:80g:10g. First, furanol, poloxamer, and ethanol were added sequentially to deionized water, and mechanically stirred for 5 minutes at 250 rpm. Then, hydrochloric acid was added, and stirring continued for 10 minutes. The temperature was then gradually increased to 80℃, and the reaction was allowed to proceed for 1 hour. Next, 160g of sulfuric acid (5mol / L) was added for inerting at 100℃ for 3 hours. After the reaction was complete, the reaction product was washed with deionized water until neutral, aged at room temperature for 1 day, and then dried at 85℃ for 20 hours to obtain polyfuranol resin microspheres. The polyfuranol resin microspheres were then pyrolyzed into glassy carbon microspheres at 800℃ for 1 hour. The glassy carbon microspheres were then activated to prepare porous glassy carbon microspheres. KHCO3 was used as the activator. The mass ratio of activator to glassy carbon microspheres was 3:1. The activation temperature was 800℃, and the activation time was 1 hour.
[0051] Example 10
[0052] Materials were added according to the mass ratio of furanol:poloxamer:deionized water:ethanol:hydrochloric acid = 20g:10g:80g:80g:10g. First, furanol, poloxamer, and ethanol were added sequentially to deionized water, and mechanically stirred for 5 minutes at 250 rpm. Then, hydrochloric acid was added, and stirring continued for 10 minutes. The temperature was then gradually increased to 80℃, and the reaction was allowed to proceed for 1 hour. Next, 100g of sulfuric acid (5mol / L) was added for inerting at 100℃ for 1 hour. After the reaction was complete, the reaction product was washed with deionized water until neutral, aged at room temperature for 1 day, and then dried at 85℃ for 20 hours to obtain polyfuranol resin microspheres. The polyfuranol resin microspheres were then pyrolyzed into glassy carbon microspheres at 800℃ for 1 hour. The glassy carbon microspheres were then activated to prepare porous glassy carbon microspheres. NaHCO3 was used as the activator. The mass ratio of activator to glassy carbon microspheres was 3:1. The activation temperature was 800℃, and the activation time was 1 hour.
[0053] Example 11
[0054] Materials were added according to the mass ratio of furanol:poloxamer:deionized water:ethanol:hydrochloric acid = 20g:10g:80g:80g:10g. First, furanol, poloxamer, and ethanol were added sequentially to deionized water, and mechanically stirred for 5 minutes at 250 rpm. Then, hydrochloric acid was added, and stirring continued for 10 minutes. The temperature was then gradually increased to 80℃, and the reaction was allowed to proceed for 1 hour. Next, 100g of sulfuric acid (5mol / L) was added for inerting at 100℃ for 3 hours. After the reaction was complete, the reaction product was washed with deionized water until neutral, aged at room temperature for 1 day, and then dried at 85℃ for 20 hours to obtain polyfuranol resin microspheres. The polyfuranol resin microspheres were then pyrolyzed into glassy carbon microspheres at 800℃ for 1 hour. The glassy carbon microspheres were then activated to prepare porous glassy carbon microspheres. CaCO3 was used as the activator. The mass ratio of activator to glassy carbon microspheres was 3:1. The activation temperature was 800℃, and the activation time was 1 hour.
[0055] Example 12
[0056] Materials were added according to the mass ratio of furanol:poloxamer:deionized water:ethanol:hydrochloric acid = 20g:10g:80g:80g:10g. First, furanol, poloxamer, and ethanol were added sequentially to deionized water, and mechanically stirred for 5 minutes at 250 rpm. Then, hydrochloric acid was added, and stirring continued for 10 minutes. The temperature was then gradually increased to 80℃, and the reaction was allowed to proceed for 1 hour. Next, 100g of sulfuric acid (5mol / L) was added for inerting at 100℃ for 3 hours. After the reaction was complete, the reaction product was washed with deionized water until neutral, aged at room temperature for 1 day, and then dried at 85℃ for 20 hours to obtain polyfuranol resin microspheres. The polyfuranol resin microspheres were then pyrolyzed into glassy carbon microspheres at 800℃ for 1 hour. The glassy carbon microspheres were then activated to prepare porous glassy carbon microspheres using NiCl2·6H2O as the activator. The mass ratio of activator to glassy carbon microspheres was 3:1. The activation temperature was 800℃, and the activation time was 1 hour.
[0057] Table 1 shows the pore structure analysis results of the porous glassy carbon microspheres prepared in Example 7.
[0058] Table 1 Table 1 sample <![CDATA[S BET (m 2 / g)]]> <![CDATA[V total (cm 3 / g)]]> <![CDATA[D DFT (nm)]]> Example 7 1378 1.0 1.4
[0059] Among them, V total Total pore volume when P / P0 = 0.99; S BET : BET specific surface area; D DFT : Aperture calculated by NLDFT method.
[0060] Comparative Example 1
[0061] Materials were added according to the mass ratio of furanol:poloxamer:deionized water:ethanol:hydrochloric acid = 20g:10g:80g:80g:10g. First, furanol, poloxamer, and ethanol were added sequentially to deionized water, and mechanically stirred for 5 minutes at 250 rpm. Then, hydrochloric acid was added, and stirring continued for 10 minutes. The temperature was then gradually increased to 80℃, and the reaction was allowed to proceed for 1 hour. After the reaction was complete, the reaction product was washed with deionized water until neutral, aged at room temperature for 1 day, and then dried at 85℃ for 20 hours to obtain polyfuranol resin microspheres. The polyfuranol resin microspheres were then pyrolyzed into glassy carbon microspheres. The pyrolysis temperature was 800℃, and the pyrolysis time was 1 hour. The glassy carbon microspheres were then activated to prepare porous glassy carbon microspheres. KHCO3 was used as the activator. The mass ratio of activator to glassy carbon microspheres was 3:1. The activation temperature was 800℃, and the activation time was 1 hour. Figure 5 It can be seen that the comparative example did not use sulfuric acid for inerting treatment, resulting in poor dispersibility of the glassy carbon microspheres.
[0062] Comparative Example 2
[0063] Materials were added according to the mass ratio of furanol:poloxamer:deionized water:ethanol:hydrochloric acid = 20g:10g:80g:80g:10g. First, furanol, poloxamer, and ethanol were added sequentially to deionized water, and mechanically stirred for 5 minutes at 250 rpm. Then, hydrochloric acid was added, and stirring continued for 10 minutes. The temperature was then gradually increased to 80℃, and the reaction was allowed to proceed for 1 hour. Next, 120g of sulfuric acid (5mol / L) was added for inerting at 100℃ for 1 hour. After the reaction was complete, the reaction product was washed with deionized water until neutral, aged at room temperature for 1 day, and then dried at 85℃ for 20 hours to obtain polyfuranol resin microspheres. The polyfuranol resin microspheres were then pyrolyzed into glassy carbon microspheres at 800℃ for 1 hour. The glassy carbon microspheres were then activated to prepare porous glassy carbon microspheres. KHCO3 was used as the activator. The mass ratio of activator to glassy carbon microspheres was 3:1. The activation temperature was 800℃, and the activation time was 1 hour. Figure 6 It can be seen that a shorter inerting time results in poor dispersibility of the glassy carbon microspheres.
Claims
1. A method for preparing polyfuran-methanol resin-derived porous glassy carbon microspheres, characterized in that, include: Step (1) uses furanol as a reactant and causes it to undergo a polymerization reaction under the action of surfactant and acid catalyst; Step (2) inertizes the polymerization product with an inertizing agent. Step (3) Wash the inerted product until neutral, and after aging and drying, obtain polyfuran methanol resin microspheres; Step (4) Crack the polyfuran methanol resin microspheres to obtain glassy carbon microspheres. Step (5) activate the glassy carbon microspheres to obtain porous glassy carbon microspheres.
2. The preparation method according to claim 1, characterized in that, In step (1), the acid catalyst includes inorganic acid and organic acid; preferably, the mass ratio of acid catalyst to furan-methanol is (0.1-3):1; more preferably, the acid catalyst is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, lactic acid, and oxalic acid.
3. The preparation method according to claim 1 or 2, characterized in that, In step (1), the surfactant is poloxamer; preferably, the mass ratio of the surfactant to furanol is (0.1-3):
1.
4. The preparation method according to any one of claims 1 to 3, characterized in that, In step (1), the polymerization reaction temperature is 60-90℃ and the polymerization reaction time is 1-5h.
5. The preparation method according to any one of claims 1 to 4, characterized in that, In step (2), the inerting agent is 1-10 mol / L sulfuric acid; preferably, the mass ratio of the inerting agent to furanol is (1-10):
1.
6. The preparation method according to any one of claims 1 to 5, characterized in that, In step (2), the inerting temperature is 60-120℃ and the inerting time is 0.5-5h.
7. The preparation method according to any one of claims 1 to 6, characterized in that, In step (3), the aging temperature is room temperature and the aging time is 12 to 36 hours.
8. The preparation method according to any one of claims 1 to 7, characterized in that, In step (3), the drying temperature is 60-95℃ and the drying time is 12-48h.
9. The preparation method according to any one of claims 1 to 8, characterized in that, In step (4), the pyrolysis temperature is 700-1100℃ and the pyrolysis time is 1-5h.
10. The preparation method according to any one of claims 1 to 9, characterized in that, In step (5), the activator is selected from at least one of potassium bicarbonate, sodium bicarbonate, calcium carbonate, nickel chloride or their hydrates; preferably, the mass ratio of the activator to the glassy carbon microspheres is (1-5):1; more preferably, the activation temperature is 700-1100℃ and the activation time is 1-5h.