CN113149003A - In-situ ultra-small zinc nanocrystalline template method for synthesizing nitrogen-doped porous carbon, method and application - Google Patents
In-situ ultra-small zinc nanocrystalline template method for synthesizing nitrogen-doped porous carbon, method and application Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 80
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 45
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 43
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000003763 carbonization Methods 0.000 claims abstract description 28
- 229920003228 poly(4-vinyl pyridine) Polymers 0.000 claims abstract description 28
- 239000011148 porous material Substances 0.000 claims abstract description 27
- 239000011592 zinc chloride Substances 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000003463 adsorbent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims abstract description 5
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 25
- 239000012065 filter cake Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000010000 carbonizing Methods 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000002159 nanocrystal Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 29
- 239000007789 gas Substances 0.000 abstract description 20
- 238000009826 distribution Methods 0.000 abstract description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 42
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 27
- 235000005074 zinc chloride Nutrition 0.000 description 21
- 239000000203 mixture Substances 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 239000003575 carbonaceous material Substances 0.000 description 13
- 238000000926 separation method Methods 0.000 description 12
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- 239000002243 precursor Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
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- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- B01D53/02—Separation 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 adsorption, e.g. preparative gas chromatography
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Abstract
The invention relates to a method for synthesizing nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method, and a method and application thereof, wherein the method uses P4VP and ZnCl2Is taken as a raw material and is carbonized and acid etched; based on P4VP and Zn2+Interaction control of Zn during carbonization2+Thermal stability to P4VP, ZnCl during carbonization2Firstly, converting the ZnO nanocluster into a ZnO nanocluster, reacting the ZnO nanocluster with surrounding C atoms to consume a part of carbon, and converting the ZnO nanocluster into a gaseous simple substance Zn to leave to generate a pore structure; the remaining ZnO or elemental Zn is removed during acid etching to further create a pore structure. Compared with the prior art, the nitrogen-doped porous carbon has the advantages of large specific surface area, high nitrogen doping amount, concentrated pore size distribution and the like; c which is excellent as a gas adsorbent2H2、C2H6、C3H8And CO2Ultra high adsorption capacity, ultra high x/CH4And CO2/N2IAST selectivity.
Description
Technical Field
The invention belongs to the technical field of gas adsorption separation materials, and particularly relates to a method for synthesizing nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method, and a method and application thereof.
Background
Carbon materials have been widely used in environmental protection, catalysis, and energy storage/conversion due to their high electron mobility, excellent weatherability, environmental friendliness, and low cost. Especially, the application performance of the porous carbon material with abundant pore structure, large specific surface area and proper heteroatom doping becomes more prominent and competitive. For example, nitrogen-doped porous carbon (NDPCs) having a high surface area exhibit gas adsorption separation performance comparable to that of Porous Coordination Polymers (PCPs) and Metal Organic Frameworks (MOFs).
The choice of raw materials has a significant impact on the performance of the material, and a variety of carbon material precursors have been developed and reported over the past few decades, from natural products to synthetic organic molecules, and from small organic molecules to polymers. Unfortunately, most organic molecules are thermally less stable and completely evaporate or decompose even in an inert atmosphere, resulting in a very limited range of carbon source choices to date. In addition, the synthesis of carbon materials should avoid complicated processes or harsh conditions, in view of the requirements of practical applications. Therefore, it is of great significance to develop a simple and effective method to assist the carbon conversion of thermally unstable organic molecules and synthesize high-performance carbon materials. In this regard, the subject groups of Dai and Antonietti [ Lee J S, Wang X Q, Luo H M, et al].Journal of the American Chemical Society 2009,131:4596-4597；Wang X,Dai S.Ionic liquids as versatile precursors for functionalized porous carbon and carbon-oxide composite materials by confined carbonization[J].Angewandte Chemie International Edition 2010, 49:6664-6668；Paraknowitsch J P,Zhang J,Su D,et al.Ionic liquids as precursors for nitrogen-doped graphitic carbon[J].Advanced Materials 2010,22:87-92]Each independently finds a strategy for synthesizing carbon materials from ionic liquids, but this strategy is only applicable to a few expensive ionic liquids containing crosslinking functional groups (such as cyano or nitrile groups). Watanabe topic group [ Zhang S, Miran M S, Ikoma A, et al].Journal of the American Chemical Society 2014,136:1690-1693；Zhang S,Dokko K,Watanabe M.Direct synthesis of nitrogen-doped carbon materials from protic ionic liquids and protic salts: structural and physicochemical correlations between precursor and carbon[J].Chemistry of Materials 2014,26:2915-2926]Reported as H2SO4A strategy for synthesizing carbon material by protonating ionic liquid. But this strategy is limited to obtaining non-metallic doped carbon materials.
Disclosure of Invention
The invention aims to provide a method for synthesizing nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method, and a method and application thereof. The nitrogen-doped porous carbon (Zn-NDPC) has the advantages of large specific surface area, high nitrogen doping amount, concentrated pore size distribution and the like; Zn-NDPC shows excellent C as a gas adsorbent2H2、C2H6、C3H8And CO2Adsorption capacity and ultra-high x/CH4And CO2/N2IAST selectivity.
The invention is achieved by transition metal cations (Zn)2+) Directly synthesizing nitrogen-doped porous carbon material by auxiliary carbonization of thermally unstable organic polymer (P4VP) and reacting with CoCl2·6H2O and CuCl2·2H2The pore-forming mechanisms such as O and the like are obviously different.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a method for synthesizing nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method, which uses poly 4-vinylpyridine (P4VP) and zinc chloride (ZnCl)2) Is taken as a raw material and is carbonized and acid etched; based on P4VP and Zn2 +Interaction control of Zn during carbonization2+Thermal stability to P4VP, ZnCl during carbonization2Firstly, converting the ZnO nanocluster into a ZnO nanocluster, reacting the ZnO nanocluster with surrounding C atoms to consume a part of carbon, and converting the ZnO nanocluster into a gaseous simple substance Zn to leave to generate a pore structure; and removing residual ZnO or simple substance Zn in the carbonization process in the acid etching process to further generate a pore structure, thus obtaining the in-situ ultra-small zinc nanocrystalline template method for synthesizing the nitrogen-doped porous carbon.
Preferably, the method comprises the steps of:
(a) poly-4-vinylpyridine (P4VP) and zinc chloride (ZnCl)2) Mixing the components in a solvent, stirring, and distilling under reduced pressure to obtain a coordination compound Zn-P4VP；
(b) In N2Carbonizing Zn-P4VP under the atmosphere to obtain Zn/nitrogen-doped carbon composite material Zn-NDC;
(c) washing the Zn-NDC with an acid to remove the residual Zn template therein;
(d) and washing the acid-washed Zn-NDC with deionized water to be neutral, filtering to obtain a filter cake, and drying the filter cake to obtain Zn-NDPC, namely the nitrogen-doped porous carbon.
Preferably, in step (a), said P4VP is reacted with ZnCl2The mass ratio of (A) to (B) is 0.1-1.0: 0.5-5.0; zn in complex Zn-P4VP2+The molar ratio of/N is 2; the solvent is absolute ethyl alcohol.
Preferably, in the step (b), the carbonization temperature is 500-800 ℃ and the time is 1-4 h; the heating rate is 2.5-7.5 ℃ per minute-1。
Preferably, in the step (c), the acid is hydrochloric acid, the concentration of the hydrochloric acid is 0.5-2.5M, and the washing time is 5-24 h.
Preferably, in the step (d), the drying temperature is 40-80 ℃ and the drying time is 12-36 h.
The invention provides a nitrogen-doped porous carbon synthesized by an in-situ ultra-small zinc nanocrystalline template method, and the nitrogen-doped porous carbon is prepared by the method.
The specific surface area of the porous carbon is 600-1500 m2·g-1The volume of the micro-pores is 0.35-0.85 cm3·g-1The nitrogen doping amount (atomic percentage) is 6 to 11 at%, and the pore diameter is 0.3 to 2.0 nm.
More preferably, the specific surface area of the porous carbon is 900-1200 m2·g-1The volume of the micro-pores is 0.45-0.65 cm3·g-1The nitrogen doping amount (atomic percentage) is 7 to 9 at%, and the aperture is 0.4 to 1.0 nm.
The third aspect of the invention provides the application of the in-situ ultra-small zinc nanocrystalline template method in synthesizing nitrogen-doped porous carbon, and the nitrogen-doped porous carbon is used as an adsorbent for C2H2、C2H6、C3H8And CO2Adsorbing and having x/CH4And CO2/N2IAST selectivity ofX includes C2H2、C2H6、C3H8Or CO2。
Optimally, at 298K and 1bar, nitrogen-doped porous carbon (Zn-NDPC) exhibits excellent C2H2、C2H6、C3H8And CO2The adsorption capacities were 3.2, 2.7, 4.8 and 2.5 mmol/g, respectively-1And ultra high x/CH4(x＝C2H2、C2H6、C3H8Or CO2) And CO2/N2IAST selectivities 33.4, 20.3, 404.6, 11.3, and 63.9.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a catalyst based on poly-4-vinylpyridine (P4VP) and zinc chloride (ZnCl)2) Preparation method for synthesizing nitrogen-doped porous carbon (Zn-NDPC) by using raw materials, and the preparation method is based on P4VP and Zn2+Interaction during carbonization to control metal cations (Zn)2+) Thermal stability to P4VP, ZnCl during carbonization2Firstly, converting the ZnO nanocluster into a ZnO nanocluster, reacting the ZnO nanocluster with surrounding C atoms to consume a part of carbon, and converting the ZnO nanocluster into a gaseous simple substance Zn to leave to generate a pore structure; the residual ZnO or elemental Zn during carbonization is removed during acid etching to further create a pore structure. The zinc nanoclusters simultaneously play a role in dual pore-forming of an activating agent and a template agent in the preparation process of the Zn-NDPC.
2. The nitrogen-doped porous carbon (Zn-NDPC) synthesized by the in-situ and ultra-small zinc nanocrystalline template method has a large specific surface area (900-1200 m)2·g-1) The volume of the macro-micro pores is 0.45-0.65 cm3·g-1) High nitrogen doping amount (7-9 at%), and concentrated aperture distribution (0.4-1.0 nm).
3. The nitrogen-doped porous carbon material synthesized by the in-situ and ultra-small zinc nanocrystalline template method prepared by the invention has high C2H2、C2H6、C3H8And CO2Adsorption capacity and ultra-high x/CH4And CO2/N2IAST selectivity has high application value in the field of gas adsorption and separation. As adsorbent, Zn-NDPC showed excellent C at 298K and 1bar2H2、C2H6、C3H8And CO2The adsorption capacities were 3.2, 2.7, 4.8 and 2.5 mmol/g, respectively-1And ultra high x/CH4(x＝C2H2、C2H6、C3H8And CO2) And CO2/N2IAST selectivities 33.4, 20.3, 404.6, 11.3, and 63.9.
Drawings
FIG. 1 is a schematic diagram of a process for preparing Zn-NDPC;
FIG. 2 is (a, d) Zn-NDC-500; (b, e) Zn-NDPC-500; (c, f) TEM picture of Zn-NDC-800; illustration is shown: FFT images obtained from the respective marker regions;
FIG. 3 shows (a, b) N of Zn-NDPC2Adsorption isotherms; (c, d) NLDFT pore size distribution curve.
Detailed Description
A method for synthesizing nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method is provided, wherein poly 4-vinylpyridine (P4VP) and zinc chloride (ZnCl) are used in the method2) Is taken as a raw material and is carbonized and acid etched; based on P4VP and Zn2+Interaction control of Zn during carbonization2+Thermal stability to P4VP, ZnCl during carbonization2Firstly, converting the ZnO nanocluster into a ZnO nanocluster, reacting the ZnO nanocluster with surrounding C atoms to consume a part of carbon, and converting the ZnO nanocluster into a gaseous simple substance Zn to leave to generate a pore structure; and removing residual ZnO or simple substance Zn in the carbonization process in the acid etching process to further generate a pore structure, thus obtaining the in-situ ultra-small zinc nanocrystalline template method for synthesizing the nitrogen-doped porous carbon.
More specifically, the method comprises the steps of:
(a) poly-4-vinylpyridine (P4VP) and zinc chloride (ZnCl)2) Mixing the components in a solvent, stirring, and then distilling under reduced pressure to obtain a coordination compound Zn-P4 VP;
(b) in N2Carbonizing Zn-P4VP under atmosphere to obtain Zn/nitrogen doped carbon compositeThe material Zn-NDC-X (X stands for carbonization temperature, such as 500, 600, 700 and 800 ℃;
(c) washing the Zn-NDC with an acid to remove the residual Zn template therein;
(d) and washing the acid-washed Zn-NDC with deionized water to be neutral, filtering to obtain a filter cake, and drying the filter cake to obtain Zn-NDPC, namely the nitrogen-doped porous carbon.
In step (a), P4VP and ZnCl are preferred2The mass ratio of (A) to (B) is 0.1-1.0: 0.5-5.0; zn in complex Zn-P4VP2+The molar ratio/N was 2. The solvent is preferably absolute ethanol.
In the step (b), the carbonization temperature is preferably 500-800 ℃ for 1-4 h; the heating rate is 2.5-7.5 ℃ per minute-1。
In the step (c), preferably, the acid is hydrochloric acid, the concentration of the hydrochloric acid is 0.5-2.5M, and the washing time is 5-24 h.
In the step (d), the drying temperature is preferably 40-80 ℃ and the time is 12-36 h.
The nitrogen-doped porous carbon is synthesized by adopting the in-situ ultra-small zinc nanocrystalline template method prepared by the method. The specific surface area of the porous carbon is 600-1500 m2·g-1The volume of the micro-pores is 0.35-0.85 cm3·g-1The nitrogen doping amount is 6 to 11 at%, and the pore diameter is 0.3 to 2.0 nm. Preferably, the specific surface area of the porous carbon is 900-1200 m2·g-1The volume of the micro-pores is 0.45-0.65 cm3·g-1The nitrogen doping amount is 7 to 9 at%, and the pore diameter is 0.4 to 1.0 nm.
The nitrogen-doped porous carbon synthesized by the in-situ ultra-small zinc nanocrystalline template method can be used as an adsorbent for C2H2、C2H6、C3H8And CO2Adsorbing and having x/CH4And CO2/N2IAST selectivity, said x comprising C2H2、C2H6、C3H8Or CO2。
The method for evaluating the gas adsorption separation performance comprises the following steps:
1. static adsorption Capacity test of samples at 0 and 25 deg.C
Sample pair CH at 0 and 25 ℃4、C2H2、C2H6、C3H8、CO2And N2The static adsorption test of (2) is characterized by an Autosorb-iQ2 specific surface area and a pore diameter adsorption instrument. The test range is 0-1 bar, the ice-water mixture is used as a test thermostat at 0 ℃, the water at 25 ℃ is used as a test thermostat at 25 ℃, and the mass of the sample is about 100 mg. The samples were degassed at 250 ℃ for 12h before testing.
Sample cycle stability was evaluated by conducting 5 consecutive adsorption-desorption experiments on an Autosorb-iQ2 adsorber. The sample was degassed just before the start of the first adsorption test and weighed at the end of each desorption to correct for the sample mass. The removal of gas between different cycles depends on the vacuum pumping process of the apparatus.
2. Adsorption data single point Langmuir-Freundlich model fit:
b is a temperature-related parameter, which is related as follows:
R＝8.314J mol-1K-1。
3. gas adsorption selectivity prediction
The prediction of the adsorption selectivity (S) of the sample for different gases is calculated according to the Ideal Adsorption Solution Theory (IAST) and is calculated according to the following formula:
in the above formula xiAnd yiRepresents the molar fraction of i component (i ═ 1,2) in the adsorption and bulk phases, respectively, of the sample at adsorption equilibrium.
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A method for synthesizing nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method comprises the following steps: a) 0.42g P4VP and 1.09g ZnCl were mixed2Mixing the two solutions, stirring the mixture in 200mL of absolute ethanol for 4 hours, and then distilling the mixture under reduced pressure to obtain a coordination compound Zn-P4VP (Zn)2+The molar ratio/N is 2); b) in N2Carbonizing Zn-P4VP at 500 deg.C for 2h under atmosphere to obtain Zn/nitrogen doped carbon composite material Zn-NDC-500(500 represents carbonization temperature 500 deg.C; heating rate 5 deg.C. min.)-1) (ii) a c) Washing the Zn-NDC-50012 h with 200mL of hydrochloric acid (1M) to remove the residual Zn template; d) and washing the acid-washed Zn-NDC with deionized water to be neutral, filtering to obtain a filter cake, and drying the filter cake in a 60 ℃ oven for 24 hours to obtain the Zn-NDPC-500. The nitrogen-doped porous carbon synthesized by the in-situ ultra-small zinc nanocrystalline template method is subjected to structure characterization and gas adsorption separation performance test, and the results are shown in tables 1-4.
Example 2
A method for synthesizing nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method comprises the following steps: a) 0.42g P4VP and 1.09g ZnCl were mixed2Mixing the two solutions, stirring the mixture in 200mL of absolute ethanol for 4 hours, and then distilling the mixture under reduced pressure to obtain a coordination compound Zn-P4VP (Zn)2+The molar ratio/N is 2); b) in N2Carbonizing Zn-P4VP at 600 deg.C for 2h under atmosphere to obtain Zn/nitrogen doped carbon composite material Zn-NDC-600(600 represents carbonization temperature 600 deg.C; heating rate 5 deg.C. min.)-1) (ii) a c) Washing the Zn-NDC-60012 h with 200mL hydrochloric acid (1M) to remove the residual Zn template; d) and washing the acid-washed Zn-NDC with deionized water to be neutral, filtering to obtain a filter cake, and drying the filter cake in a 60 ℃ oven for 24 hours to obtain the Zn-NDPC-600. The nitrogen-doped porous carbon synthesized by the in-situ ultra-small zinc nanocrystalline template method is subjected to structure characterization and gas adsorption separation performance test, and the results are shown in tables 1-4.
Example 3
A method for synthesizing nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method comprises the following steps: a) 0.42g P4VP and 1.09g ZnCl were mixed2Mixing the two solutions, stirring the mixture in 200mL of absolute ethanol for 4 hours, and then distilling the mixture under reduced pressure to obtain a coordination compound Zn-P4VP (Zn)2+The molar ratio/N is 2); b) in N2Carbonizing Zn-P4VP at 700 deg.C for 2h under atmosphere to obtain Zn/nitrogen doped carbon composite material Zn-NDC-700(700 represents carbonization temperature 700 deg.C; heating rate 5 deg.C. min.)-1) (ii) a c) Washing the Zn-NDC-70012 h with 200mL of hydrochloric acid (1M) to remove the residual Zn template; d) and washing the acid-washed Zn-NDC with deionized water to be neutral, filtering to obtain a filter cake, and drying the filter cake in a 60 ℃ oven for 24 hours to obtain the Zn-NDPC-700. The nitrogen-doped porous carbon synthesized by the in-situ ultra-small zinc nanocrystalline template method is subjected to structure characterization and gas adsorption separation performance test, and the results are shown in tables 1-4.
Example 4
A method for synthesizing nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method comprises the following steps: a) 0.42g P4VP and 1.09g ZnCl were mixed2Mixing the two solutions, stirring the mixture in 200mL of absolute ethanol for 4 hours, and then distilling the mixture under reduced pressure to obtain a coordination compound Zn-P4VP (Zn)2+The molar ratio/N is 2); b) in N2Carbonizing Zn-P4VP at 800 deg.C for 2h under atmosphere to obtain Zn/nitrogen doped carbon composite material Zn-NDC-800(800 represents carbonization temperature 800 deg.C; heating rate 5 deg.C. min.)-1) (ii) a c) Washing the Zn-NDC-80012 h with 200mL of hydrochloric acid (1M) to remove residual Zn template; d) and washing the acid-washed Zn-NDC with deionized water to be neutral, filtering to obtain a filter cake, and drying the filter cake in a 60 ℃ oven for 24 hours to obtain the Zn-NDPC-800. The nitrogen-doped porous carbon synthesized by the in-situ ultra-small zinc nanocrystalline template method is subjected to structure characterization and gas adsorption separation performance test, and the results are shown in tables 1-4.
TABLE 1 organizational Structure characteristics and metallic Zn content of Zn-NDPCs
The element content is as follows: (a) XPS (at%), (b) ICP-AES (wt%).
TABLE 2 examples gas loading at 273 or 298K, 1bar
TABLE 3 example at 298K, 1bar vs. x/CH4IAST selectivity of (50/50, v/v) binary gas mixture
TABLE 4 example at 298K, 1bar vs. CO2/N2(v/v) IAST Selectivity of binary gas mixture
Example 5
A method for synthesizing nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method comprises the following steps: a) 0.84g P4VP and 2.18g ZnCl were mixed2The mixture was stirred in 300mL of absolute ethanol for 4 hours, and then distilled under reduced pressure to obtain a complex Zn-P4VP (Zn)2+The molar ratio/N is 2); b) in N2Carbonizing Zn-P4VP at 500 deg.C for 3h under atmosphere to obtain Zn/nitrogen doped carbon composite material Zn-NDC-500(500 represents carbonization temperature 500 deg.C; heating rate 5 deg.C. min.)-1) (ii) a c) Washing the Zn-NDC-50018 h with 300mL of hydrochloric acid (1M) to remove residual Zn template; d) and washing the acid-washed Zn-NDC with deionized water to be neutral, filtering to obtain a filter cake, and drying the filter cake in a 60 ℃ oven for 36 hours to obtain the Zn-NDPC-500. And synthesizing the nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method to test the gas adsorption separation performance.
Example 6
A method for synthesizing nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method comprises the following steps: a) 0.21g P4VP and 0.545g ZnCl2Mixing the two solutions, stirring the mixture in 200mL of absolute ethanol for 4 hours, and then distilling the mixture under reduced pressure to obtain a coordination compound Zn-P4VP (Zn)2+The molar ratio/N is 2); b) in N2Carbonizing Zn-P4VP at 500 deg.C for 2h under atmosphere to obtain Zn/nitrogen doped carbon composite material Zn-NDC-500(500 represents carbonization temperature 500 deg.C; heating rate 5 deg.C. min.)-1) (ii) a c) Washing the Zn-NDC-50012 h with 200mL of hydrochloric acid (1M) to remove the residual Zn template; d) and washing the acid-washed Zn-NDC with deionized water to be neutral, filtering to obtain a filter cake, and drying the filter cake in a 60 ℃ oven for 24 hours to obtain the Zn-NDPC-500. And synthesizing the nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method to test the gas adsorption separation performance.
Example 7
A method for synthesizing nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method comprises the following steps: a) 0.42g P4VP and 1.09g ZnCl were mixed2Mixing the two solutions, stirring the mixture in 200mL of absolute ethanol for 4 hours, and then distilling the mixture under reduced pressure to obtain a coordination compound Zn-P4VP (Zn)2+The molar ratio/N is 2); b) in N2Carbonizing Zn-P4VP at 500 deg.C for 2h under atmosphere to obtain Zn/N doped carbon composite material Zn-NDC-500(500 represents carbonization temperature 500 deg.C; heating rate 2.5 deg.C. min)-1) (ii) a c) Washing the Zn-NDC-50012 h with 200mL of hydrochloric acid (1M) to remove the residual Zn template; d) and washing the acid-washed Zn-NDC with deionized water to be neutral, filtering to obtain a filter cake, and drying the filter cake in a 60 ℃ oven for 24 hours to obtain the Zn-NDPC-500. And synthesizing the nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method to test the gas adsorption separation performance.
Example 8
A method for synthesizing nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method comprises the following steps: a) 0.42g P4VP and 1.09g ZnCl were mixed2Mixing the two solutions, stirring the mixture in 200mL of absolute ethanol for 4 hours, and then distilling the mixture under reduced pressure to obtain a coordination compound Zn-P4VP (Zn)2+The molar ratio/N is 2); b) in N2Carbonizing Zn-P4VP at 500 deg.C for 2h under atmosphere to obtain Zn/N doped carbon composite material Zn-NDC-500(500 represents carbonization temperature 500 deg.C; heating rate 7.5 deg.C. min.)-1) (ii) a c) Washing with 200mL of hydrochloric acid (1M)The Zn-NDC-50012 h is used for removing the residual Zn template; d) and washing the acid-washed Zn-NDC with deionized water to be neutral, filtering to obtain a filter cake, and drying the filter cake in a 60 ℃ oven for 24 hours to obtain the Zn-NDPC-500. And synthesizing the nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method to test the gas adsorption separation performance.
A schematic diagram of the process for preparing Zn-NDPC according to the present invention is shown in FIG. 1, FIG. 2(a, d) Zn-NDC-500; (b, e) Zn-NDPC-500; (c, f) TEM picture of Zn-NDC-800; illustration is shown: FFT images obtained from the respective marker regions.
In summary, as shown in FIGS. 1-3 and tables 1-4, with P4VP and ZnCl2The nitrogen-doped porous carbon material (Zn-NDPC) is successfully synthesized by an in-situ and ultra-small zinc nanocrystalline template method. The thermally labile organic molecule P4VP is completely decomposed even in an inert atmosphere, but reacts with Zn2+The mixture can be successfully converted into a carbon material to show Zn2+The thermal stability of P4VP is obviously improved, and the metallic cation Zn is proved2+Positive catalytic action on carbon conversion of thermally unstable organic molecules. The zinc nanoclusters simultaneously play a role in dual pore-forming of an activating agent and a template agent in the whole preparation process of the Zn-NDPC. As adsorbent, the sample of example 1(Zn-NDPC-500) showed excellent C at 298K and 1bar2H2、C2H6、C3H8And CO2The adsorption capacities were 3.2, 2.7, 4.8 and 2.5 mmol/g, respectively-1And ultra high x/CH4(x＝C2H2、C2H6、C3H8And CO2) And CO2/N2IAST selectivities 33.4, 20.3, 404.6, 11.3, and 63.9.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for synthesizing nitrogen-doped porous carbon by an in-situ ultra-small zinc nanocrystalline template method is characterized in that P4VP and ZnCl are adopted in the method2Is taken as a raw material and is carbonized and acid etched; based on P4VP and Zn2+Interaction control of Zn during carbonization2+Thermal stability to P4VP, ZnCl during carbonization2Firstly, converting the ZnO nanocluster into a ZnO nanocluster, reacting the ZnO nanocluster with surrounding C atoms to consume a part of carbon, and converting the ZnO nanocluster into a gaseous simple substance Zn to leave to generate a pore structure; and removing residual ZnO or simple substance Zn in the carbonization process in the acid etching process to further generate a pore structure, thus obtaining the in-situ ultra-small zinc nanocrystalline template method for synthesizing the nitrogen-doped porous carbon.
2. The method for synthesizing nitrogen-doped porous carbon by using the in-situ ultra-small zinc nanocrystalline template method according to claim 1, characterized by comprising the following steps:
(a) reacting P4VP with ZnCl2Mixing the components in a solvent, stirring, and then distilling under reduced pressure to obtain a coordination compound Zn-P4 VP;
(b) in N2Carbonizing Zn-P4VP under the atmosphere to obtain Zn/nitrogen-doped carbon composite material Zn-NDC;
(c) washing the Zn-NDC with an acid to remove the residual Zn template therein;
(d) and washing the acid-washed Zn-NDC with deionized water to be neutral, filtering to obtain a filter cake, and drying the filter cake to obtain Zn-NDPC, namely the nitrogen-doped porous carbon.
3. The method for synthesizing nitrogen-doped porous carbon by using the in-situ ultra-small zinc nanocrystal template method as claimed in claim 2, wherein in step (a), P4VP and ZnCl are added2The mass ratio of (A) to (B) is 0.1-1.0: 0.5-5.0; zn in complex Zn-P4VP2+The molar ratio of/N is 2; the solvent is absolute ethyl alcohol.
4. The in-situ ultra-small zinc nanocrystalline die according to claim 2The method for synthesizing the nitrogen-doped porous carbon by the plate method is characterized in that in the step (b), the carbonization temperature is 500-800 ℃, and the time is 1-4 h; the heating rate is 2.5-7.5 ℃ per minute-1。
5. The method for synthesizing nitrogen-doped porous carbon by using the in-situ ultra-small zinc nanocrystalline template method according to claim 2, wherein in the step (c), the acid is hydrochloric acid, the concentration of the hydrochloric acid is 0.5-2.5M, and the washing time is 5-24 h.
6. The method for synthesizing nitrogen-doped porous carbon by using the in-situ ultra-small zinc nanocrystalline template method according to claim 2, wherein in the step (d), the drying temperature is 40-80 ℃ and the drying time is 12-36 h.
7. An in-situ ultra-small zinc nanocrystalline template method for synthesizing nitrogen-doped porous carbon, which is characterized by being prepared by the method of any one of claims 1 to 6.
8. The in-situ synthesis of nitrogen-doped porous carbon by using the ultra-small zinc nanocrystalline template method according to claim 7, wherein the specific surface area of the porous carbon is 600-1500 m2·g-1The volume of the micro-pores is 0.35-0.85 cm3·g-1The nitrogen doping amount is 6 to 11 at%, and the pore diameter is 0.3 to 2.0 nm.
9. The in-situ synthesis of nitrogen-doped porous carbon by using the ultra-small zinc nanocrystalline template method according to claim 8, wherein the specific surface area of the porous carbon is 900-1200 m2·g-1The volume of the micro-pores is 0.45-0.65 cm3·g-1The nitrogen doping amount is 7 to 9 at%, and the pore diameter is 0.4 to 1.0 nm.
10. Application of the in-situ ultra-small zinc nanocrystalline template method for synthesizing nitrogen-doped porous carbon according to any one of claims 7 to 9, characterized in that the nitrogen-doped porous carbon is used as an adsorbent for C2H2、C2H6、C3H8And CO2Adsorbing and having x/CH4And CO2/N2IAST selectivity, said x comprising C2H2、C2H6、C3H8Or CO2。
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