CN112897484A - g-C without defect3N4Nanosheets, two-dimensional g-C3N4Nano sheet film, preparation method and application - Google Patents

g-C without defect3N4Nanosheets, two-dimensional g-C3N4Nano sheet film, preparation method and application Download PDF

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CN112897484A
CN112897484A CN202110051238.7A CN202110051238A CN112897484A CN 112897484 A CN112897484 A CN 112897484A CN 202110051238 A CN202110051238 A CN 202110051238A CN 112897484 A CN112897484 A CN 112897484A
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薛健
周燚洒
张娅
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South China University of Technology SCUT
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/06Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
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    • B01D53/22Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039Inorganic membrane manufacture
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract

The invention discloses a defect-free g-C3N4Nanosheets, two-dimensional g-C3N4A nano-sheet film, a preparation method and application. The preparation steps are as follows: dissolving melamine and phosphoric acid in water, carrying out hydrothermal treatment, filtering, and carrying out heating reflux treatment on the layered micro-rod precursor by taking a mixture of polyhydric alcohol and ethanol as an insert; cleaning, drying, heating and sintering in inert atmosphereObtaining g-C free of defects3N4Nanosheets; then the nano-sheets are dispersed in a solvent, and the two-dimensional g-C for gas separation is obtained by depositing the nano-sheets on a substrate in a simple vacuum filtration mode3N4A nanoplatelet film. The assembled membrane of the invention shows excellent gas separation performance, and the hydrogen permeation can reach 7.23 multiplied by 10‑7mol m‑2s‑1Pa‑1Applied to the separation of hydrogen from gas molecules of different kinetic diameters, H2/CO2The selectivity can reach 30.2, H2/C3H6The selectivity is over hundred, and the method has wide application prospect.

Description

g-C without defect3N4Nanosheets, two-dimensional g-C3N4Nano sheet film, preparation method and application
Technical Field
The invention belongs to the technical field of gas membrane separation, and particularly relates to a defect-free g-C3N4Nanosheets, two-dimensional g-C3N4A nano-sheet film, a preparation method and application.
Background
Gas separation is widely used in industrial processes such as hydrogen recovery, carbon capture and storage, natural gas upgrading, alkane recovery, benzene derivative separation, air purification and the like. Common techniques used in these processes include cryogenic distillation, and absorption and adsorption, as well as the use of membrane technology. Processes that rely on heat, such as distillation and absorption, account for over 10% of the world's energy consumption, increase global emissions and pollution, and membrane-based separation processes do not require heating and are therefore a competitive gas separation process. About 90% of the costs associated with heat generation will be saved by replacing the distillation process with membrane separation technology. In addition, membrane separation has other inherent advantages such as less environmental pollution (NO emissions), continuous operation, and simplicity.
Conventional polymer or zeolite membranes suffer from a tradeoff between permeability and selectivity (i.e., the upper robertson limit). Emerging two-dimensional (2D) nanoflake support membranes are expected to overcome this limitation due to their ultra-thin thickness and tunable sieving channels. Membranes composed of these nanomaterials perform much better than conventional membranes and exhibit mass transfer separation mechanisms that are quite different from conventional membranes. Among these, two-dimensional separation membranes typified by graphene (graphene) and derivatives thereof are most prominent. But the gas permeation quantity of the graphene-based film is still kept at 10 due to low pore density and long interlayer transmission channels-7(mol m-2s-1Pa-1) The magnitude is still at a lower level, and the industrial requirements cannot be met. Two-dimensional graphitic carbon nitride (g-C)3N4) The nanoplatelets have a graphene-like layered structure, enabling their use in membrane separation processes. And intrinsic in-plane nanopores
Figure BDA0002899127440000011
Distributed uniformly and at high density throughout the planar network, these nanopores can be used not only for sieving small gas molecules but also to greatly shorten the gas transport path of the membrane. But at present g-C3N4Most of the nano sheets are obtained by a mode of peeling from top to bottom, and in the process, a plane heptazine ring unit is easily damaged, so that g-C is caused3N4Large defects (greater than) appear in the nanosheets
Figure BDA0002899127440000021
) And cannot be used for gas separation. For example, Wang et al will find g-C obtained by exfoliation3N4The nano sheet has defect holes of 1-3 nm, and the two-dimensional film obtained by assembly provides more transmission channels for water molecules but cannot be used for gas separation, and only has g-C without defects3N4The nanosheets can be used to prepare gas sieving membranes.
Disclosure of Invention
To overcome the disadvantages and shortcomings of the prior art, an improved bottom-up method is used to obtain high quality defect free g-C3N4Nanosheets. In the synthesis process from bottom to top, organic solvent molecules are inserted into the assembled layered precursor in advance, and the thermal polymerization can obtain a flawless thin layer g-C3N4Nanosheets, g-C3N4The nano-sheets are layered into thin-layer nano-sheets in the thermal polycondensation process. Therefore, no further exfoliation is required, and hence the generation of non-selective defects due to structural damage can be largely avoided. Based on defect-free g-C3N4Nanosheets, assembled with g-C for gas separation by vacuum filtration3N4A nanoplatelet film. The primary object of the present invention is to prepare defect-free g-C3N4The nano-sheet and the membrane assembled by the nano-sheet can be applied to the field of gas separation. The invention provides a defect-free g-C3N4Nanosheets, two-dimensional g-C3N4A nano-sheet film, a preparation method and application.
The purpose of the invention is realized by the following technical scheme.
g-C without defect3N4A method of making nanoplatelets comprising the steps of:
(1) adding melamine and phosphoric acid into deionized water, and carrying out constant-temperature water bath until the solid is completely dissolved;
(2) carrying out hydrothermal treatment on the solution obtained in the step (1), and filtering to obtain a layered micro-rod precursor;
(3) washing the laminar micro-rod precursor obtained in the step (2) with deionized water for 2-3 times, and then drying at 60-80 ℃ to obtain white powder;
(4) heating and refluxing the white powder obtained in the step (3) by taking a mixture of polyhydric alcohol and ethanol as an intercalation agent to obtain layered precursor powder after organic solvent molecule intercalation; washing the layered precursor powder with ethanol, and then drying at 60-80 ℃;
(5) sintering the dried layered precursor powder in the step (4) under the inert gas atmosphere (stripping and plane polymerization) to obtain g-C with no defects3N4Nanosheets.
Preferably, in the step (1), the molar ratio of the melamine to the phosphoric acid is 1: 1-2: 1, the temperature of the constant-temperature water bath is 70-90 ℃, and the time of the constant-temperature water bath is 0.5-1 h; in the step (2), the hydrothermal treatment time is 10-12 h, and the hydrothermal treatment temperature is 160-180 ℃.
Preferably, in the step (4), the polyol is glycerol, the volume ratio of the polyol to the ethanol in the mixed solution is 2: 1-3: 1, and the temperature of the reflux treatment is 80-90 ℃; the time of the reflux treatment is 2-4 h; further preferably, the volume ratio of the polyhydric alcohol to the ethanol in the mixed solution is 2: 1.
Preferably, in the step (5), the inert gas is nitrogen,the flow rate of the inert gas is 100-200 mL/min; the sintering temperature is 520-550 ℃, the sintering time is 2-4 h, and the sintering temperature rise rate is 2-5 ℃/min; further preferably, the temperature increase rate of sintering is 2 ℃/min. g-C is caused by the ammonia gas obtained during the decomposition of melamine3N4Defects are generated, and more complete g-C can be obtained by driving off the generated ammonia gas in an inert atmosphere3N4A nanopore structure. Therefore, we chose inert nitrogen operating conditions.
Defect-free g-C prepared by the above preparation method3N4Nanosheets.
Two-dimensional g-C3N4The preparation method of the nanosheet membrane comprises the following steps:
(a) the above-mentioned defect-free g-C3N4Dispersing the nano-sheets in a mixed solution of deionized water and isopropanol to obtain g-C3N4A nanosheet suspension;
(b) subjecting g-C as described in step (a)3N4The nanosheet suspension is filtered under vacuum conditions using a porous support, and g-C is prepared on the porous support3N4A film;
(c) subjecting g-C as described in step (b)3N4Drying the membrane in vacuum to obtain the two-dimensional g-C loaded on the porous carrier3N4A nanoplatelet film.
Preferably, in the step (a), the volume ratio of deionized water to isopropanol in the mixed solution is 1: 1-3: 1, and the g-C is3N4g-C in nanosheet suspension3N4The concentration of the nano sheet is 0.005-0.02 mg/mL; further preferably, the volume ratio of the deionized water to the isopropanol in the mixed solution is 1:1(v: v).
Preferably, in the step (b), the porous carrier is an anodic aluminum oxide film AAO, and the pore diameter of the porous carrier is 160-200 nm; in the step (c), the vacuum drying time is more than 24 hours, and the vacuum drying temperature is room temperature.
Two-dimensional g-C prepared by the above preparation method3N4Nanoplatelets film, said two-dimensional g-C3N4The thickness of the nanosheet film is 0.15-1 μm.
Two-dimensional g-C as described above3N4The application of the nano-sheet membrane in the field of gas separation.
Preferably, the specific application process is as follows: subjecting the resulting g-C3N4The membrane was encapsulated with a domestic Wicke-Kallenbach apparatus for gas testing. Gas molecules (H) of different kinetic diameters2,CO2,N2,CH4,C3H6,C3H8) By said g-C3N4Nanoplatelet membranes, membrane pairs H2/CO2The selectivity can reach 30.2, H2/C3H6The selectivity is over one hundred.
Compared with the prior art, the invention has the following advantages:
(1) g-C obtained3N4The nanosheets are defect-free, and the assembled membrane can be used for separating gas molecules with smaller sizes
Figure BDA0002899127440000041
(2) g-C obtained3N4The nano-sheet membrane has ultrahigh hydrogen flux and excellent stability, and the hydrogen permeation can reach 7.23 multiplied by 10-7mol m-2s-1Pa-1The method meets the requirements in the industrial production process and has wide application prospect.
(3) g-C obtained3N4The nanosheet membrane exhibits excellent gas separation performance, and is applied to separation of hydrogen and gas molecules with different kinetic diameters, H2/CO2The selectivity can reach 30.2, H2/C3H6The selectivity is over one hundred.
Drawings
FIG. 1 is a graph showing defect-free g-C obtained in example 13N4SEM and AFM images (a) and (b) of the nanoplatelets.
FIG. 2 is a graph of two-dimensional g-C obtained in example 13N4SEM images of (a) surface and (b) cross-section of the nanoplatelets film.
FIG. 3 is the two-dimensional g-C obtained in example 13N4The nanoplatelets films are used for single gas performance maps in various gas molecule tests.
FIG. 4 is a graph of two-dimensional g-C obtained in example 13N4Stability profile of nanoplatelets films for up to 300 days of continuous operation.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the embodiments and the protection scope of the present invention are not limited thereto.
Example 1
g-C without defect3N4Nanosheets, two-dimensional g-C3N4The preparation method of the nanosheet membrane specifically comprises the following steps:
(1) synthesizing a layered precursor: 1.0g of melamine and 1.2g of phosphoric acid are first weighed, mixed with 100ml of deionized water and heated in a thermostatic water bath at 80 ℃ for 1h until the melamine and the phosphoric acid are completely dissolved. And then transferring the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene substrate while the solution is hot, and reacting at 180 ℃ for 12h to obtain a layered micro-rod precursor. Filtering, washing the mixture obtained after hydrothermal treatment with deionized water for several times, and drying in a drying oven at 60 ℃ for 10h to obtain white powder, namely a layered precursor;
(2) synthesizing a layered precursor after organic solvent molecule intercalation: the layered precursor obtained previously was heated under reflux at 90 ℃ for 3 hours with 20ml of a mixed solution of ethanol and glycerol (2:1, v: v). Washing the powder obtained after refluxing for multiple times by using ethanol, and drying in an oven at 60 ℃ for 10 hours to obtain a layered precursor after organic solvent molecule intercalation;
(3) preparation of defect-free g-C3N4Nanosheet: in N2Under the condition (100mL/min), heating the layered precursor after the organic solvent molecule intercalation to 550 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 2h to obtain the defect-free g-C3N4Nanosheets;
for g-C obtained in step (3)3N4g-C in two-dimensional nanosheet solution3N4SEM and AFM tests of the two-dimensional nanosheets, and resultsAs shown in fig. 1, it can be seen from fig. 1 that: g-C3N4The two-dimensional nano-sheets have no defects, and the thickness of the nano-sheets is about 3 nm.
(4) Preparation of g-C3N4Nano-sheet film: taking 1mg of the obtained g-C3N4The nanoplatelets were dispersed in 50ml of a mixed solution of deionized water and isopropanol at a ratio of 1:1(v: v). To obtain g-C with a concentration of 0.02mg/mL3N4A nanosheet suspension. Filtering a certain amount of g-C by a vacuum filtration system3N4The nanosheet suspension is prepared by preparing g-C with different thicknesses on an anodic alumina carrier with the aperture of 160-200 nm3N4And (3) a membrane. Vacuum drying the membrane obtained by suction filtration at room temperature for more than 24h to remove residual solvent in the membrane to obtain the two-dimensional g-C loaded on the porous carrier3N4A nanoplatelet film.
For g-C with different thicknesses obtained in the step (4)3N4The two-dimensional nanoplatelets film was SEM tested and the results are shown in fig. 2, from which fig. 2 it can be seen that: the film surface was intact with no detectable pinholes or cracks.
For g-C obtained in step (4)3N4The two-dimensional nanosheet membrane was subjected to a gas separation test, the results of which are shown in fig. 3, and it can be seen from fig. 3 that: g-C3N4The single gas transmission of hydrogen, carbon dioxide, nitrogen, methane, propylene and propane of the two-dimensional nanosheet membrane is 7.24 × 10-7mol m-2s-1Pa-1、2.93×10-8mol m-2s-1Pa-1、6.09×10-8mol m-2s-1Pa-1、5.93×10- 8mol m-2s-1Pa-1、8.59×10-9mol m-2s-1Pa-1And 6.59X 10-9mol m-2s-1Pa-1。H2To CO2、CH4、N2、C3H6And C3H8The selectivities of (a) were 30.2, 14, 15, 103.6 and 135, respectively, far exceeding the corresponding Knudsen diffusions.
For g-C obtained in step (4)3N4Two-dimensional nanoplatelet membrane for H2/CO2The stability test results are shown in fig. 4, and it can be seen from fig. 4 that: the membrane was stable in separation performance in a three hundred day long term test, even when stored in the environment for 200 days without introducing any protective gas.
Example 2
g-C without defect3N4Nanosheets, two-dimensional g-C3N4The preparation method of the nanosheet membrane specifically comprises the following steps:
(1) synthesizing a layered precursor: 1.12g of melamine and 1.23g of phosphoric acid are initially weighed, mixed with 50ml of deionized water and heated in a thermostatic water bath at 80 ℃ for 0.5 h. And then transferring the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene substrate while the solution is hot, and reacting for 10 hours at 180 ℃ to obtain a layered micro-rod precursor. Washing the mixture obtained after hydrothermal treatment with deionized water for several times, and drying in a drying oven at 60 ℃ for 10h to obtain white powder, namely a layered precursor;
(2) synthesizing a layered precursor after organic solvent molecule intercalation: the layered precursor obtained previously was heated under reflux at 90 ℃ for 2 hours with 20ml of a mixed solution of ethanol and glycerol (2:1, v: v). Washing the powder obtained after refluxing for multiple times by using ethanol, and drying in an oven at 60 ℃ for 12 hours to obtain a layered precursor after organic solvent molecule intercalation;
(3) preparation of defect-free g-C3N4Nanosheet: in N2Under the condition (200mL/min), heating the layered precursor after the organic solvent molecule intercalation to 520 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 4h to obtain the defect-free g-C3N4Nanosheets;
(4) preparation of g-C3N4Nano-sheet film: taking 1mg of the obtained g-C3N4The nanoplatelets were dispersed in 50ml of a mixed solution of deionized water and isopropanol in a ratio of 2:1(v: v). To obtain g-C with a concentration of 0.02mg/mL3N4A nanosheet suspension. Filtering a certain amount of g-C by a vacuum filtration system3N4The nanosheet suspension is prepared by preparing g-doped alumina with different thicknesses on an anodic alumina carrier with the aperture of 160-200 nmC3N4And (3) a membrane. Vacuum drying the membrane obtained by suction filtration at room temperature for more than 24h to remove residual solvent in the membrane to obtain the two-dimensional g-C loaded on the porous carrier3N4A nanoplatelet film.
Example 3
g-C without defect3N4Nanosheets, two-dimensional g-C3N4The preparation method of the nanosheet membrane specifically comprises the following steps:
(1) synthesizing a layered precursor: 1.05g of melamine and 1.27g of phosphoric acid are first weighed, mixed with 100ml of deionized water and heated in a thermostatic water bath at 80 ℃ for 1h until the melamine is completely dissolved. And then transferring the solution into a hydrothermal reaction kettle with a polytetrafluoroethylene substrate while the solution is hot, and reacting for 10 hours at 180 ℃ to obtain a layered micro-rod precursor. Washing the mixture obtained after hydrothermal treatment with deionized water for several times, and drying in a drying oven at 60 ℃ for 10h to obtain white powder, namely a layered precursor;
(2) synthesizing a layered precursor after organic solvent molecule intercalation: the layered precursor obtained previously was heated under reflux at 90 ℃ for 4 hours with 20ml of a mixed solution of ethanol and glycerol (2:1, v: v). Washing the powder obtained after refluxing for multiple times by using ethanol, and drying in an oven at 60 ℃ for 13h to obtain a layered precursor after organic solvent molecule intercalation;
(3) preparation of defect-free g-C3N4Nanosheet: in N2Under the condition (150mL/min), heating the layered precursor after the organic solvent molecule intercalation to 520 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 2h to obtain the defect-free g-C3N4Nanosheets;
(4) preparation of g-C3N4Nano-sheet film: taking 0.5mg of the obtained g-C3N4The nanoplatelets were dispersed in 50ml of a mixed solution of deionized water and isopropanol in a ratio of 3:1(v: v). To obtain g-C with a concentration of 0.01mg/mL3N4A nanosheet suspension. Filtering a certain amount of g-C by a vacuum filtration system3N4The nanosheet suspension is prepared by preparing g-C with different thicknesses on an anodic alumina carrier with the aperture of 160-200 nm3N4And (3) a membrane.Vacuum drying the membrane obtained by suction filtration at room temperature for more than 24h to remove residual solvent in the membrane to obtain the two-dimensional g-C loaded on the porous carrier3N4A nanoplatelet film.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, combinations, modifications, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, combinations, modifications, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. g-C without defect3N4The preparation method of the nanosheet is characterized by comprising the following steps:
(1) adding melamine and phosphoric acid into deionized water, and carrying out constant-temperature water bath until the solid is completely dissolved;
(2) carrying out hydrothermal treatment on the solution obtained in the step (1), and filtering to obtain a layered micro-rod precursor;
(3) washing the laminar micro-rod precursor obtained in the step (2) with deionized water for 2-3 times, and then drying at 60-80 ℃ to obtain white powder;
(4) heating and refluxing the white powder obtained in the step (3) by taking a mixture of polyhydric alcohol and ethanol as an intercalation agent to obtain layered precursor powder after organic solvent molecule intercalation; washing the layered precursor powder with ethanol, and then drying at 60-80 ℃;
(5) sintering the dried layered precursor powder in the step (4) under the inert gas atmosphere condition to obtain flawless g-C3N4Nanosheets.
2. The preparation method according to claim 1, wherein in the step (1), the molar ratio of the melamine to the phosphoric acid is 1: 1-2: 1, the temperature of the thermostatic water bath is 70-90 ℃, and the time of the thermostatic water bath is 0.5-1 h; in the step (2), the hydrothermal treatment time is 10-12 h, and the hydrothermal treatment temperature is 160-180 ℃.
3. The preparation method according to claim 1, wherein in the step (4), the polyol is glycerol, the volume ratio of the polyol to the ethanol in the mixed solution is 2:1 to 3:1, and the temperature of the reflux treatment is 80 to 90 ℃; the time of the reflux treatment is 2-4 h.
4. The method as claimed in claim 1, wherein in the step (5), the inert gas is nitrogen, and the flow rate of the inert gas is 100-200 mL/min; the sintering temperature is 520-550 ℃, the sintering time is 2-4 h, and the sintering temperature rise rate is 2-5 ℃/min.
5. Defect-free g-C prepared by the preparation method of any one of claims 1 to 43N4Nanosheets.
6. Two-dimensional g-C3N4The preparation method of the nanosheet membrane is characterized by comprising the following steps of:
(a) the defect-free g-C of claim 53N4Dispersing the nano-sheets in a mixed solution of deionized water and isopropanol to obtain g-C3N4A nanosheet suspension;
(b) subjecting g-C as described in step (a)3N4The nanosheet suspension is filtered under vacuum conditions using a porous support, and g-C is prepared on the porous support3N4A film;
(c) subjecting g-C as described in step (b)3N4Drying the membrane in vacuum to obtain the two-dimensional g-C loaded on the porous carrier3N4A nanoplatelet film.
7. The preparation method according to claim 6, wherein in the step (a), the volume ratio of the deionized water to the isopropanol in the mixed solution is 1: 1-3: 1, and the g-C is3N4g-C in nanosheet suspension3N4The concentration of the nano sheet is 0.005-0.02 mg/mL.
8. The preparation method according to claim 6, wherein in the step (b), the porous carrier is an anodic aluminum oxide film (AAO), and the pore diameter of the porous carrier is 160-200 nm; in the step (c), the vacuum drying time is more than 24 hours, and the vacuum drying temperature is room temperature.
9. Two-dimensional g-C prepared by the preparation method of any one of claims 6 to 83N4Nanoplatelets film characterized in that said two-dimensional g-C3N4The thickness of the nanosheet film is 0.15-1 μm.
10. The two-dimensional g-C of claim 93N4The application of the nano-sheet membrane in the field of gas separation.
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