CN108380180B - Mineral acid intercalation graphene oxide CO2Preparation method of adsorbing material - Google Patents

Mineral acid intercalation graphene oxide CO2Preparation method of adsorbing material Download PDF

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CN108380180B
CN108380180B CN201810234350.2A CN201810234350A CN108380180B CN 108380180 B CN108380180 B CN 108380180B CN 201810234350 A CN201810234350 A CN 201810234350A CN 108380180 B CN108380180 B CN 108380180B
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graphene oxide
mineral acid
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oxide material
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CN108380180A (en
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徐静
刘海军
李静
赵联明
邢伟
朱后禹
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China University of Petroleum East China
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Abstract

The invention discloses a mineral acid intercalated graphene oxide CO2A preparation method of the adsorbing material. The method takes graphene oxide as a precursor and takes mineral acid with different concentrations as guest molecules to intercalate the graphene oxide, so as to prepare a series of materials with CO2Mineral acid intercalation graphene oxide material with adsorption performance. The method comprises the steps of preparing graphene oxide, preparing a mineral acid intercalated graphene oxide material, and carrying out CO synthesis on the structure and the CO of the mineral acid intercalated graphene oxide material2And (5) an adsorption property characterization step. The mineral acid raw material adopted by the invention has low price, simple and easy operation, easy synthesis, suitability for mass production and important application value.

Description

Mineral acid intercalation graphene oxide CO2Preparation method of adsorbing material
Technical Field
The invention relates to preparation of a graphene oxide intercalation material, in particular to a graphene oxide intercalation material with CO2A preparation method of a gas adsorption property mineral acid intercalation graphene oxide material.
Background
Carbon dioxide (CO) produced by excessive fossil energy consumption2) Is the main component of greenhouse gas and also is the main factor influencing global warming, and the human society more and more urgently hopes to greatly reduce CO2And the emission of greenhouse gases. Currently, the capture method commonly used in the industryIs prepared by mixing CO2Introducing amine solution, reacting with amine molecules, and washing CO2. However, this method is highly toxic, costly, and has a low adsorption/desorption rate. In contrast, adsorption separation is receiving more and more attention due to its advantages such as large storage capacity, good reversibility of gas adsorption and desorption, and low energy consumption. The technical key of the adsorption separation is to select a proper adsorbent material. Among various adsorbent materials, graphene has an ultra-light mass density and an ultra-large specific surface area (2600 m)2g-1) And the chemically modifiable nature of the surface, show great potential for gas capture.
The graphene sheets have strong intermolecular force among the layers, so that the sheets are easily stacked together and are difficult to disperse, and a graphite structure with the interlayer spacing of only 0.334nm is formed. The specific surface area of the material is greatly reduced due to the characteristic of stacking of graphene sheets, and the efficient utilization of an interface is limited. In order to obtain an ideal graphene gas adsorption material, guest molecules can be inserted between graphene sheets to expand the distance between graphene layers and improve the specific surface area of the material. For example, terpyridine intercalated graphene-terpyridine complexes [ Carbon,2014,66: 592-]And aliphatic diamine (NH)2(CH2)nNH2N-4, 8,12) intercalated multilayer graphene oxide [ Nanoscale Research Letters,2015,10:318]. However, the graphene intercalation material prepared at present has poor thermal stability and the specific surface area of the material can not reach the theoretical value (2600 m)2g-1) The gas adsorption capacity is small, and the guest molecules (columns) for graphene intercalation are expensive, which is not favorable for commercial large-scale application.
CO of graphene intercalation materials2The gas adsorption performance is closely related to the nature of the inserted guest molecule. On the one hand, the more guest molecules are inserted, the more effective the interlayer spacing can be expanded, and the stability of the system can be increased. However, when the number of intercalated molecules is too large, the porosity and specific surface area of the system are reduced, and the gas adsorption capacity is lowered. On the other hand, due to CO2Has stronger polarizability (29.11 × 10)25cm3) And a four dipole moment (4.30 × 10)26esu cm) so as to insertAdding strongly polar guest molecules to increase CO2The adsorption capacity of the molecule.
Mineral acids such as sulfuric acid and phosphoric acid have the advantages of large molecular structure, strong polarity, low price and the like, so that the graphene oxide intercalation material prepared by intercalating the graphene oxide by taking the mineral acids such as sulfuric acid and phosphoric acid as guest molecules has strong CO2The adsorption capacity and the cost are low, and the method is beneficial to commercial application. At present, no research case for preparing a graphene oxide intercalation material by intercalating graphene oxide with mineral acid exists internationally.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a mineral acid intercalated graphene oxide CO2A preparation method of the adsorbing material. The method takes cheap mineral acid as guest molecule to react with graphene oxide to prepare the graphite oxide intercalation material, and characterizes the structure and CO of the material2Gas adsorption performance.
The purpose of the invention is realized by the following technical scheme:
mineral acid intercalation graphene oxide CO2The preparation method of the adsorbing material comprises the following steps:
(1) preparation of graphene oxide
Graphene Oxide (GO) is prepared by adopting an improved Hummers method. Adding 2g of crystalline flake graphite and 1g of sodium nitrate into a three-neck flask; 46ml of concentrated sulfuric acid was added thereto in an ice water bath and sufficiently stirred. 6g of potassium permanganate is added, and the reaction is continued for 3 hours. Heating to 35 deg.C, and stirring for 30 min; adding 92ml of deionized water dropwise, raising the temperature of the water bath to 98 ℃, and stirring for 20 min; 280ml of deionized water with the temperature of 70 ℃ is added, and then 20ml of hydrogen peroxide is added and stirred for 15 minutes. And repeatedly washing and vacuum drying the product to obtain GO.
(2) Preparation of mineral acid intercalation graphene oxide material
6.06mg ml of the solution is prepared-1The prepared GO solution is subjected to ultrasonic treatment for 2-3 hours, water is changed every 20 minutes, the ultrasonic machine is turned off for half an hour every hour, and after the seismic source is completely cooled down, the ultrasonic treatment is started againAnd (4) sound. 2.4ml of mineral acid solution was dropped drop wise into a beaker with GO solution and stirred continuously on a magnetic stirrer for 24h, then filtered. And drying the filtered sample at 40 ℃ in vacuum to obtain the mineral acid intercalated graphene oxide material.
(3) Structure and CO of mineral acid intercalated graphene oxide material2Characterization of adsorption Properties
The oxidation of graphite was characterized by X-ray powder diffraction (XRD) and the interlayer spacing of the graphene oxide material after mineral acid intercalation was determined. Functional groups (such as sulfate, phosphate and hydroxyl groups) contained in the mineral acid intercalated graphene oxide material are determined by Fourier infrared spectroscopy (FT-IR) analysis. By N2Measuring the BET specific surface area of the mineral acid intercalated graphene oxide material by adsorption; by CO2Adsorption determination of CO in mineral acid intercalated graphene oxide material2Adsorption capacity.
The invention has the advantages and effects that: the invention overcomes the defects of high price, complex preparation process, strict operating environment requirement and the like of the existing graphene intercalation material, adopts the mineral acid raw material with low price, has simple adopted process, simple and easy operation, easy synthesis and suitability for mass production, and has important application value.
Drawings
FIG. 1 is a mineral acid intercalated graphene oxide CO2Detailed steps of the method for preparing the adsorbent are shown.
Fig. 2 is an X-ray diffraction pattern of graphene oxide and sulfuric acid intercalated graphite oxide material.
Fig. 3 is a fourier transform-infrared spectrum of a graphene oxide and sulfuric acid intercalated graphite oxide material.
FIG. 4 is CO of a sulfuric acid intercalated graphite oxide material2Adsorption isotherms.
Fig. 5 is an X-ray diffraction pattern of graphene oxide and phosphoric acid intercalated graphite oxide material.
Fig. 6 is a fourier transform-infrared spectrum of a graphene oxide and phosphoric acid intercalated graphite oxide material.
FIG. 7 is CO of phosphoric acid intercalated graphite oxide material2Adsorption isotherms.
Detailed Description
The invention relates to a mineral acid intercalated graphene oxide CO2The detailed steps of the preparation method of the adsorbing material are shown in fig. 1, and the following takes the sulfuric acid intercalated graphene oxide material and the phosphoric acid intercalated graphene oxide material as examples to describe the invention in detail. It is to be understood that the following is illustrative of the present invention only and is not intended to limit the scope of the present invention.
Example 1 sulfuric acid intercalated graphene oxide CO2Preparation method of adsorbing material
(1) Preparation of graphene oxide
Graphene Oxide (GO) was prepared by a modified Hummers method, namely:
1g of sodium nitrate and 2g of flake graphite are put into a 500mL three-neck flask; slowly adding 46mL of concentrated sulfuric acid into the three-neck flask under the condition of ice-water bath, and fully stirring for 10 min; measuring 6g of potassium permanganate, slowly adding the potassium permanganate into a reaction flask in multiple times, and starting timing reaction for 3 hours after the potassium permanganate is added; then removing the ice water bath, heating the water in the water bath to 35 ℃, and continuing stirring for 30 min; after the medium temperature reaction is finished, 92mL of deionized water with the temperature of 70 ℃ in the reaction flask is added dropwise, the temperature of the water bath is increased to 98 ℃, the reaction flask is taken out of the water bath after being stirred for 20min, and the product in the reaction flask is transferred to a larger beaker (900 mL).
Deionized water (280mL, 70 ℃) and hydrogen peroxide (20mL, 30%) are respectively added into the solution, and then stirring is continued for 15 minutes to reduce the residual oxidant, so that the reaction is stopped; centrifuging the product at 9000r min-1Centrifuging (first centrifugation for 5 min, then gradually increasing the centrifugation time), washing repeatedly, and washing every 2 hr until the filtrate is neutral and free of SO42-(ii) present; and (3) putting the product into a surface dish, and carrying out vacuum drying for 48h at 55 ℃, wherein the dried product is GO.
(2) Preparation of sulfuric acid intercalation graphene oxide material
6.06mg ml was made up using 200mg GO and 33ml deionized water-1Then carrying out ultrasonic treatment on the prepared GO solution for 2.5 hours, changing water every 20 minutes, and closing every hourAnd (5) dropping the ultrasonic machine for half an hour, and restarting the ultrasonic after the seismic source is completely cooled down.
20ml of 0.5mol/L, 1mol/L and 5mol/L sulfuric acid solutions are prepared respectively as representatives; 2.4ml of the prepared sulfuric acid solution is dropwise added into a beaker filled with the GO solution and is continuously stirred on a magnetic stirrer. And continuously stirring the obtained mixed solution for 24 hours, then filtering, and finally drying the sample in vacuum at 40 ℃ to obtain the sulfuric acid intercalated graphene oxide material.
(3) Structure and CO of sulfuric acid intercalated graphene oxide material2Characterization of adsorption Properties
The sulfuric acid intercalation graphene oxide materials generated by 0.5mol/L, 1mol/L and 5mol/L sulfuric acid solutions and graphene oxide are respectively named as IGO-S-M, wherein M is 0.5,1 and 5. The X-ray powder diffraction (XRD) spectra of GO and IGO-S-M are shown in FIG. 2. The XRD spectrum shows a sharp strong graphene oxide diffraction peak at 2 theta 12.2 deg. and no graphite diffraction peak near 2 theta 26.5 deg., indicating that the graphite has been completely oxidized, and the interlayer spacing is enlarged from 0.34nm to 0.72nm due to the generation of a large number of oxygen-containing groups on both sides of the graphene sheet during oxidation. After the sulfuric acid intercalation, the diffraction peaks of IGO-S-M, M ═ 0.5,1 and 5 appeared at 11.4 °, 11.3 ° and 9.2 °, respectively, indicating that the distance between graphene oxide layers increased to 0.77nm for IGO-S-0.5, 0.78nm for IGO-S-1 and 0.95nm for IGO-S-5, respectively, after the sulfuric acid intercalation. The significant increase in IGO-S-M interlayer spacing relative to graphene oxide indicates successful insertion of the sulfuric acid molecules between graphene oxide lamellae.
Fourier Infrared Spectroscopy (FT-IR) is shown in FIG. 3. The graphene oxide mainly comprises 3407cm-1、1715cm-1、1429cm-1、1212 cm-1、1052cm-1、1610cm-1Six main infrared absorption peaks respectively correspond to an O-H bond stretching vibration peak, a C ═ O bond stretching vibration peak, a hydroxyl group O-H bond bending vibration peak, a C-O bond stretching vibration peak of a bridging oxygen and an alkoxy group, and a C ═ C bond stretching vibration peak. After the sulfuric acid intercalation, IGO-S-M is at 1140cm-1An additional new infrared absorption peak (see fig. 3) appears, a peak generated by sulfate oscillation, indicating that sulfuric acid has been successfully intercalated into the middle of the graphene oxide lamellae. In addition to this, the present invention is,at 1488cm-1、2851cm-1And 2945cm-1Three new infrared absorption peak peaks also appear at IGO-S-M, corresponding to bending vibration in a CH plane and CH symmetric and antisymmetric stretching vibration of alkyl, namely C ═ C bond and H on the surface of graphene oxide2SO4Addition reaction occurs to generate CHCOSO3H。
To investigate the pore structure of the material, IGO-S-M was subjected to N at 77K2And (5) performing adsorption test. From N2Adsorption-measured BET specific surface areas of IGO-S-M, M ═ 0.5,1 and 5 were 70.4M2g-1、89.2m2g-1And 141.7m2g-1. CO was performed at 273K for IGO-S-M2Adsorption test, FIG. 4 is CO2Adsorption isotherms. With the increase of the concentration of the sulfuric acid solution during intercalation, the prepared CO of IGO-S-M2The adsorption capacity sequence is: IGO-S-0.5>IGO-S-1>IGO-S-5. IGO-S-M, M is 0.5,1,5 CO when the pressure is 100kPa2The adsorption amounts were 2.3 mmol g, respectively-1、1.71mmol g-1And 1.26mmol g-1The prepared sulfuric acid intercalated graphene oxide material has high CO2And (4) adsorption performance.
Example 2 phosphoric acid intercalated graphene oxide CO2Preparation method of adsorbing material
(1) Preparation of graphene oxide
Graphene Oxide (GO) was prepared by a modified Hummers method, namely:
1g of sodium nitrate and 2g of flake graphite are put into a 500mL three-neck flask; slowly adding 46mL of concentrated sulfuric acid into the three-neck flask under the condition of ice-water bath, and fully stirring for 10 min; measuring 6g of potassium permanganate, slowly adding the potassium permanganate into a reaction flask in multiple times, and starting timing reaction for 3 hours after the potassium permanganate is added; then removing the ice water bath, heating the water in the water bath to 35 ℃, and continuing stirring for 30 min; after the medium temperature reaction is finished, 92mL of deionized water with the temperature of 70 ℃ in the reaction flask is added dropwise, the temperature of the water bath is increased to 98 ℃, the reaction flask is taken out of the water bath after being stirred for 20min, and the product in the reaction flask is transferred to a larger beaker (900 mL).
Adding deionized water into the solution respectivelyWater (280mL, 70 ℃) and hydrogen peroxide (20mL, 30%) are stirred for 15 minutes to reduce the residual oxidant and terminate the reaction; centrifuging the product at 9000r min-1Centrifuging (first centrifugation for 5 min, then gradually increasing the centrifugation time), washing repeatedly, and washing every 2 hr until the filtrate is neutral and free of SO42-(ii) present; and (3) putting the product into a surface dish, and carrying out vacuum drying for 48h at 55 ℃, wherein the dried product is GO.
(2) Preparation of phosphoric acid intercalation graphene oxide material
6.06mg ml was made up using 200mg GO and 33ml deionized water-1And then carrying out ultrasonic treatment on the prepared GO solution for 2.5h, changing water every 20 minutes, turning off the ultrasonic machine for half an hour every hour, and restarting the ultrasonic treatment after the seismic source is completely cooled down.
20ml of 0.5mol/L, 1mol/L and 5mol/L phosphoric acid solutions are prepared respectively as representatives; 2.4ml of the prepared phosphoric acid solution is dropwise added into a beaker filled with the GO solution and is continuously stirred on a magnetic stirrer. And continuously stirring the obtained mixed solution for 24 hours, then filtering, and finally drying the sample in vacuum at 40 ℃ to obtain the phosphoric acid intercalation graphene oxide material.
(3) Structure and CO of phosphoric acid intercalation graphene oxide material2Characterization of adsorption Properties
Phosphoric acid intercalation graphene oxide materials generated by 0.5mol/L, 1mol/L and 5mol/L phosphoric acid solutions and graphene oxide are respectively named as IGO-P-M, wherein M is 0.5,1 and 5. The X-ray powder diffraction (XRD) spectrum of IGO-P-M is shown in FIG. 5. After phosphoric acid intercalation, the diffraction peaks of IGO-P-M, M is 0.5,1 and 5 respectively appear at 11.7 degrees, 11.4 degrees and 10.3 degrees, and the corresponding interlayer distances are respectively 0.75nm, 0.78nm and 0.89 nm which are larger than the interlayer distance of the graphene oxide layer, thereby indicating that the phosphoric acid is successfully inserted between the graphene oxide layers.
FT-IR analysis was performed on IGO-P-M, and the specific IR spectral information is shown in FIG. 6. After phosphoric acid intercalation, IGO-P-M is at 960cm-1An additional new infrared absorption peak (see fig. 6) appears, which is the peak generated by the symmetric vibration of phosphate, indicating that phosphoric acid has been successfully inserted into the middle of the graphene oxide sheet layer. In addition, the method can be used for producing a composite materialAt 2945cm-1And 2851cm-1Two new infrared absorption peaks appear at two places of IGO-P-M at the same time, and the two new infrared absorption peaks correspond to CH symmetric and antisymmetric stretching vibration of alkyl, which is the C ═ C bond and H on the surface of graphene oxide3PO4Addition reaction occurs to generate CHCPPO3H2。
IGO-P-M was subjected to N at 77K2And (5) performing adsorption test. Warp of N2The BET specific surface areas of IGO-P-0.5, IGO-P-1 and IGO-P-5 measured by adsorption were 19.1m2g-1、40.7m2g-1And 97.3m2g-1. Measuring CO of IGO-P-M at 273K2And (4) adsorption property. FIG. 7 shows the CO of IGO-P-M at 273K2Adsorption isotherms. IGO-P-M CO2The adsorption capacity sequence is: IGO-P-0.5>IGO-P-1>IGO-P-5. CO of IGO-P-0.5, IGO-P-1 and IGO-P-5 at 100kPa2The adsorption amounts were 2.29mmol g, respectively-1、1.72mmol g-1And 1.01mmol g-1Showing that the prepared phosphoric acid intercalated graphene oxide material has strong CO2Adsorption capacity.

Claims (4)

1. Mineral acid intercalation graphene oxide CO2The preparation method of the adsorbing material is characterized by comprising the following steps:
(1) preparation of graphene oxide
Preparing Graphene Oxide (GO) by adopting an improved Hummers method; adding 2g of crystalline flake graphite and 1g of sodium nitrate into a three-neck flask; adding 46ml of concentrated sulfuric acid under the condition of ice-water bath, and fully stirring; adding 6g of potassium permanganate, and continuing to react for 3 hours; heating to 35 deg.C, and stirring for 30 min; adding 92ml of deionized water dropwise, raising the temperature of the water bath to 98 ℃, and stirring for 20 min; adding 280ml of deionized water with the temperature of 70 ℃, then adding 20ml of hydrogen peroxide and stirring for 15 minutes; repeatedly washing and vacuum drying the product to obtain GO;
(2) preparation of mineral acid intercalation graphene oxide material
Preparing a 6.06mg/mL GO water solution, then carrying out ultrasonic treatment on the prepared GO solution for 2-3 h, changing water every 20 minutes, turning off an ultrasonic machine for half an hour every hour, and restarting the ultrasonic treatment after a seismic source is completely cooled down; dropwise adding 2.4ml of mineral acid solution into a beaker filled with GO solution, continuously stirring for 24 hours on a magnetic stirrer, and then filtering; vacuum drying the filtered sample at 40 ℃ to obtain a mineral acid intercalated graphene oxide material; the mineral acid is sulfuric acid or phosphoric acid with the concentration of 0.5mol/L, 1mol/L and 5 mol/L;
(3) structure and CO of mineral acid intercalated graphene oxide material2Characterization of adsorption Properties
Characterizing the oxidation of graphite by X-ray powder diffraction (XRD) and determining the interlayer spacing of the graphene oxide material after mineral acid intercalation; determining functional groups such as sulfate groups, phosphate groups and hydroxyl groups contained in the mineral acid intercalated graphene oxide material through Fourier infrared spectroscopy (FT-IR) analysis; by N2Measuring the BET specific surface area of the mineral acid intercalated graphene oxide material by adsorption; by CO2Adsorption determination of CO in mineral acid intercalated graphene oxide material2Adsorption capacity.
2. The mineral acid intercalated graphene oxide CO according to claim 12The preparation method of the adsorbing material is characterized by comprising the following steps: the hydrogen peroxide is 30 percent.
3. The mineral acid intercalated graphene oxide CO according to claim 12The preparation method of the adsorbing material is characterized by comprising the following steps: the structural characterization means are XRD, FT-IR and N2Adsorption, characterized by XRD diffraction peaks, infrared absorption peaks and BET specific surface area.
4. The mineral acid intercalated graphene oxide CO according to claim 12The preparation method of the adsorbing material is characterized by comprising the following steps: said CO2The adsorption capacity is characterized by CO2Adsorption characterized by CO2Adsorption isotherms.
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