CN110639490A - Preparation method and application of porous carbon-based nitrogen reduction catalyst - Google Patents
Preparation method and application of porous carbon-based nitrogen reduction catalyst Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 224
- 239000003054 catalyst Substances 0.000 title claims abstract description 152
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 114
- 230000009467 reduction Effects 0.000 title claims abstract description 103
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 37
- 239000002861 polymer material Substances 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000010000 carbonizing Methods 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 238000007605 air drying Methods 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 70
- 229910021529 ammonia Inorganic materials 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 7
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- 230000001590 oxidative effect Effects 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
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- 230000007613 environmental effect Effects 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
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- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
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- 230000015572 biosynthetic process Effects 0.000 description 10
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- -1 H) in the nature2O Chemical class 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- SPBWMYPZWNFWES-UHFFFAOYSA-N disodium;azanylidyneoxidanium;iron(2+);pentacyanide;dihydrate Chemical compound O.O.[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].[O+]#N SPBWMYPZWNFWES-UHFFFAOYSA-N 0.000 description 4
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- 239000000047 product Substances 0.000 description 4
- 229960004889 salicylic acid Drugs 0.000 description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 4
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 4
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
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- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
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- 239000004570 mortar (masonry) Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
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Images
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/33—
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
Abstract
The invention discloses a preparation method and application of a porous carbon-based nitrogen reduction catalyst, wherein the preparation method comprises the steps of pretreating a high polymer raw material containing a glucose unit to obtain a pretreated high polymer material; mixing the pretreated high polymer material with a pore-forming agent and a catalyst, and carbonizing under the protection of inert gas to obtain a porous carbon material; and washing the porous carbon material with acid and deionized water in sequence, and then carrying out forced air drying to obtain the carbon-based nitrogen reduction catalyst. The invention takes macromolecules containing glucose units as raw materials, and the macromolecules are coordinated and anchored with transition metals to form monoatomic atoms, so as to obtain multiple active centers; roasting and carbonizing the pore-forming agent to obtain the porous carbon-based nitrogen reduction catalyst with high specific surface area, enhancing the nitrogen reduction performance of the carbon material non-noble metal catalyst, and realizing the preparation of the nitrogen reduction catalyst with low cost and high catalytic activity under the conditions of mildness, safety and environmental protection.
Description
Technical Field
The invention relates to the technical field of synthetic ammonia, in particular to a preparation method and application of a porous carbon-based nitrogen reduction catalyst.
Background
The great consumption of fossil fuels and the serious environmental pollution caused by the consumption of fossil fuels are attracting people's attention, and the development of renewable energy sources and conversion technologies thereof are imperative on the premise of realizing sustainable development. Electrochemical energy storage and related conversion technologies are always the hot points of research in the technical field of clean energy due to the advantages of simple operation, high energy conversion efficiency and the like. The electrochemical catalysis method is used for preparing cheap and easily-obtained small molecular compounds (such as H) in the nature2O、N2、CO2Etc.) into high value-added chemicals (e.g., H)2、NH3、CH3CH2OH, etc.) to realize efficient conversion of energy, and is a feasible path for developing new energy technology.
The annual output of ammonia, which is one of the most important chemicals at present, is at the head of various chemicals, and the synthetic ammonia is used as a high-energy-consumption industry, and the energy consumed by the industry accounts for 1-2% of the total amount of the whole world. At present, the method adopted for industrially synthesizing ammonia is still a Haber-Bosch ammonia synthesis method which is produced in the beginning of the 20 th century, and ammonia is synthesized by nitrogen and hydrogen under the conditions of high temperature, high pressure and catalyst. The Haber-Bosch method has the defects of high requirement on equipment pressure, complex process flow, low conversion rate (10-15%), high energy consumption, serious environmental pollution and the like.
The electric energy is introduced into the ammonia synthesis technology, the high reaction energy barrier of nitrogen is broken through, the attention of researchers in various countries is received all the time, and under the driving of the electric energy, the electrocatalytic ammonia synthesis can lead the thermodynamic spontaneous reaction limited by the balance to be free from or less limited by the thermodynamic balance. However, currently, the faraday efficiency of the electrochemical synthesis of ammonia is low, and through deep research on the technology of the electrocatalytic synthesis of ammonia, the development of high-efficiency catalysts and the improvement of the utilization rate of electric energy are important research hotspots of the technology of the electrocatalytic synthesis of ammonia.
The ammonia gas generation rate and the current efficiency of the electrochemical synthesis ammonia are important indexes for evaluating the quality of an electrochemical synthesis ammonia system. The catalysts that have been studied so far are mainly: pd, Ru, Fe, Pt, Ag-Pd, transition metal composite oxides, and metal-supported conductive polymers. However, none of these catalysts achieve the desired ammonia gas generation rate and current efficiency levels and are expensive.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a porous carbon-based nitrogen reduction catalyst aiming at overcoming the defects in the prior art, and the preparation method aims at solving the problems that the existing nitrogen reduction catalyst in the electrochemical synthesis of ammonia is high in manufacturing cost and low in catalytic activity.
The technical scheme adopted by the invention for solving the technical problem is as follows: a preparation method of a porous carbon-based nitrogen reduction catalyst comprises the following specific steps:
pretreating a high polymer raw material containing a glucose unit to obtain a pretreated high polymer material;
mixing the pretreated high polymer material with a pore-forming agent and a catalyst, and carbonizing under the protection of inert gas to obtain a porous carbon material;
and washing the porous carbon material with acid and deionized water in sequence, and then carrying out forced air drying to obtain the carbon-based nitrogen reduction catalyst.
The preparation method of the porous carbon-based nitrogen reduction catalyst comprises the following steps of pretreating a high polymer raw material containing a glucose unit to obtain a pretreated high polymer material:
and carrying out hydrothermal pretreatment on the high polymer raw material containing the glucose unit at 200-220 ℃ for 5-6 h to obtain a pretreated high polymer material.
The preparation method of the porous carbon-based nitrogen reduction catalyst comprises the following steps of pretreating a high polymer raw material containing a glucose unit to obtain a pretreated high polymer material:
pre-oxidizing the high polymer raw material containing the glucose unit for 1-5 hours at 200-300 ℃ to obtain a pretreated high polymer material.
The preparation method of the porous carbon-based nitrogen reduction catalyst comprises the step of preparing a porous carbon-based nitrogen reduction catalyst, wherein the pore-forming agent is one of zinc chloride and potassium hydroxide.
The preparation method of the porous carbon-based nitrogen reduction catalyst comprises the step of preparing a catalyst, wherein the catalyst is inorganic salt of transition metal.
The preparation method of the porous carbon-based nitrogen reduction catalyst comprises the step of pretreating a high polymer material, wherein the mass ratio of the pore-forming agent to the catalyst is 1:1: 1-1: 5: 5.
The preparation method of the porous carbon-based nitrogen reduction catalyst comprises the following steps of (1) carbonizing at 600-900 ℃; the carbonization time is 1-3 h; and the temperature rise rate during carbonization is 2-5 ℃/min.
The preparation method of the porous carbon-based nitrogen reduction catalyst comprises the following steps of (1) preparing an acid, wherein the acid is one of sulfuric acid and hydrochloric acid; the concentration of the acid is 0.5-3 mol/L.
The preparation method of the porous carbon-based nitrogen reduction catalyst comprises the following steps of (1) blowing and drying at the temperature of 50-100 ℃; and the air blast drying time is 6-24 h.
The application of the porous carbon-based nitrogen reduction catalyst is characterized in that the porous carbon-based nitrogen reduction catalyst prepared by the preparation method is used for synthesizing ammonia by electrocatalysis of nitrogen.
Has the advantages that: the preparation method of the invention anchors transition metal to form monoatomic atom by coordination of macromolecule containing glucose unit and containing a large amount of hydroxyl on the surface to obtain multiple active centers; the pore-forming agent is carbonized to obtain the porous carbon-based nitrogen reduction catalyst with high specific surface area, the nitrogen reduction performance of the carbon material non-noble metal catalyst is enhanced, the catalytic performance can be improved by adjusting the electronic structure of metal or carbon atoms and optimizing the adsorption/desorption of an intermediate in the preparation process, and the nitrogen reduction catalyst with low cost and high catalytic activity is prepared under the conditions of mildness, safety and environmental protection.
Drawings
FIG. 1 is a scanning electron micrograph of a porous carbon-based nitrogen reduction catalyst prepared in example 1 of the present invention;
FIG. 2 is a linear sweep voltammogram of the porous carbon-based nitrogen reduction catalyst prepared in example 1 of the present invention under nitrogen and argon atmosphere, respectively;
FIG. 3 is a scanning electron micrograph of a porous carbon-based nitrogen reduction catalyst prepared in example 2 of the present invention;
FIG. 4 is a linear sweep voltammogram of the porous carbon-based nitrogen reduction catalyst prepared in example 2 of the present invention under nitrogen and argon atmosphere, respectively;
FIG. 5 is a plot of linear sweep voltammograms of a commercial Pt/C catalyst under nitrogen and argon atmosphere, respectively;
FIG. 6 is a 0.05M solution of Na in ammonium chloride as a standard reagent2SO4Preparing ammonium chloride standard solutions of 0, 0.25, 0.5 and 1 mu g/ml in the solution respectively, and testing an ultraviolet spectrogram after a color reaction;
FIG. 7 is a standard curve obtained by plotting the absorbance at 655nm against the concentration of 0, 0.25, 0.5, 1. mu.g/ml standard solutions of ammonium chloride after color reaction;
FIG. 8 is a graph of the ultraviolet spectra of solutions of example 1, example 2 and a commercial Pt/C catalyst of the present invention after electrolysis for 2 hours in a nitrogen atmosphere, respectively, after color development;
figure 9 is a comparison of ammonia production and faraday efficiency for example 1, example 2, and commercial Pt/C catalysts of the present invention.
Detailed Description
The invention provides a preparation method of a porous carbon-based nitrogen reduction catalyst, and the invention is further described in detail below in order to make the purpose, technical scheme and advantages of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Specifically, the preparation method of the porous carbon-based nitrogen reduction catalyst comprises the following steps:
and S1, pretreating the high polymer raw material containing the glucose unit to obtain a pretreated high polymer material.
The catalysts used in the existing electrochemical synthesis of ammonia mainly comprise composite oxides of Pd, Ru, Fe, Pt, Ag-Pd and transition metals, metal-loaded conductive polymers and the like, and not only are the catalysts expensive, but also the catalysts cannot reach the ideal ammonia gas generation rate and current efficiency level. Therefore, the method takes the high polymer material containing glucose units as the raw material, adds the transition metal catalyst and the pore-forming agent, carries out roasting carbonization under the protection of inert gas, anchors the active metal on the surface of the carbon material, and obtains the multi-active center.
In a specific embodiment, the invention firstly pretreats the raw material to make the raw material molecules appropriately cross-linked and rearranged so as to improve the stability of the raw material molecules in the subsequent high-temperature roasting carbonization process. The glucose unit-containing polymer is selected as a raw material because the glucose unit-containing polymer is easily converted into carbon with high graphitization degree in the subsequent process due to the hydroxyl contained on the surface, and the higher the graphitization degree is, the better the conductivity is and the more stable the chemical property is, and the factors are beneficial to improving the electrocatalytic performance of the prepared porous carbon-based nitrogen reduction catalyst. In a specific embodiment, the raw materials are natural polymers containing glucose units, such as chitin, cyclodextrin and the like, the natural polymers are green, environment-friendly, renewable and low in cost, and the problem of high cost of the catalyst in the conventional electrochemical synthesis of ammonia is solved.
In a specific embodiment, the method for pretreating the high polymer raw material containing the glucose unit comprises a hydrothermal method and a pre-oxidation method, the pretreated high polymer material containing the glucose unit is converted into an amorphous carbon material, the carbon material in the state has a low graphitization degree, and carbon atoms bonded by sp3 bonds tend to form a sp2 hybridized carbon six-membered ring structure at high temperature, so that the pretreated high polymer material can be conveniently subjected to catalytic graphitization in subsequent steps.
In a specific embodiment, the step S1 specifically includes the steps of:
s100, carrying out hydrothermal pretreatment on the high polymer raw material containing the glucose unit at 200-220 ℃ for 5-6 h to obtain a pretreated high polymer material.
In a specific embodiment, the method adopts a hydrothermal method to pretreat the raw material, and pretreats the high molecular raw material containing glucose units under a hydrothermal condition for a period of time, so that raw material molecules are properly crosslinked and rearranged under a heated condition, and the stability of the raw material molecules in a subsequent high-temperature carbonization process is improved. In a specific embodiment, the hydrothermal temperature is 200-220 ℃, the hydrothermal time is 5-6 h, carbon with a high aromatizing degree can be formed under the condition, and the stability of the carbon in a subsequent high-temperature carbonization process is improved.
In a specific embodiment, the step S1 may further include the steps of:
s100', pre-oxidizing the high polymer raw material containing the glucose unit for 1-5 hours at 200-300 ℃ to obtain the pretreated high polymer material.
In a specific embodiment, the raw material pretreatment can also be a direct air pre-oxidation method instead of a hydrothermal method, so that the raw material is subjected to oxidative crosslinking and rearrangement among heated molecules in the air, and the stability of the raw material in the subsequent high-temperature carbonization process is improved. In a specific embodiment, the pre-oxidation temperature is 200-220 ℃, the pre-oxidation time is 5-6 h, carbon with higher aromatizing degree can be formed under the condition, and the stability of the carbon in the subsequent high-temperature carbonization process is improved.
In one embodiment, the preparation method of the porous carbon-based nitrogen reduction catalyst of the present invention further comprises the steps of:
and S2, mixing the pretreated high polymer material with a pore-forming agent and a catalyst, and carbonizing under the protection of inert gas to obtain the porous carbon material.
In a specific embodiment, after the pretreatment of the polymer raw material containing glucose units, the pretreated polymer material, the pore-forming agent and the catalyst are added into a mortar for grinding and mixing uniformly, and then high-temperature carbonization is performed in a tube furnace under the protection of inert gas. In the foregoing steps, the pretreated polymer material has an amorphous carbon structure, and under a high temperature condition, carbon atoms bonded by sp3 bonds in the raw material tend to form sp2 hybridized carbon or aromatic carbon, which can provide electron pairs to the catalyst, and the catalyst serves as an electron acceptor to anchor the active metal on the surface of the carbon material, and is converted into the carbon material completely composed of carbon six-membered rings as the carbonization time is prolonged. In a specific embodiment, the inert gas is one of nitrogen and argon.
In specific implementation, the catalyst is a graphitization catalyst, that is, the catalyst can promote graphitization of the calcined product at a lower temperature or can improve the graphitization degree of the product at the same temperature. The catalyst is transition metal inorganic salt, after the catalyst is added into the pretreated high polymer material, the high polymer material is adsorbed on the surface of the catalyst through coordination or electrostatic adsorption acting force, the carbon-containing organic matters are gradually cracked, rearranged and fused at high temperature to form large aromatic rings, and the large aromatic rings are gradually stacked to form ordered microcrystals, namely a graphitized structure. In a specific embodiment, the catalyst is cobalt chloride, and the cobalt chloride as the catalyst can be used as a graphite catalyst to improve the graphitization degree of the high polymer material on one hand, and has a pore-forming capability to improve the specific surface area and porosity of the carbonized product on the other hand; and trace cobalt remained in the porous carbon material can obviously improve the electrocatalytic performance of the carbonized product. Of course, other inorganic transition metal salts, such as FeCl, can also be used as catalysts3、NiCl2、Fe(NO3)3The present invention is not limited thereto.
In a specific embodiment, in this embodiment, a pore-forming agent is further added to the pretreated polymer material, so that micropores and mesopores are formed in the porous carbon material, thereby increasing the specific surface area of the prepared porous carbon-based nitrogen reduction catalyst, and when the catalyst is used as a nitrogen reduction catalyst, reactants can permeate into the catalyst through the micropores and the mesopores, thereby greatly improving the catalytic activity of the catalyst. In one embodiment, the pore-forming agent is one of zinc chloride and potassium hydroxide, for example, when the pore-forming agent is potassium hydroxide, the pore-forming agent potassium hydroxide etches the porous carbon material at high temperature to form carbon dioxide and carbon monoxide to generate micropores and mesopores.
In a specific embodiment, the mass ratio of the pretreated polymer material, the pore-forming agent and the catalyst is 1:1:1 to 1:5: 5. The roasting and carbonizing temperature of the pretreated high polymer material, the pore-forming agent and the catalyst is 600-900 ℃, the roasting and carbonizing time is 1-3 h, and the temperature rise rate during roasting and carbonizing is 2-5 ℃/min. Under the proportion, the prepared porous carbon material has higher specific surface area and higher graphitization degree, the high specific surface area is favorable for full contact of reactants and the catalyst, and the high graphitization degree enhances the conductivity and chemical stability of the catalyst, so that the prepared porous carbon-based nitrogen reduction catalyst has better initial potential and limiting current density compared with the existing nitrogen reduction catalyst.
In one embodiment, the preparation method of the porous carbon-based nitrogen reduction catalyst of the present invention further comprises the steps of:
and S3, washing the porous carbon material with acid and deionized water in sequence, and then drying by blowing to obtain the carbon-based nitrogen reduction catalyst.
In order to remove the excess residue in the porous carbon material, it is necessary to treat the porous carbon material with an acid after the porous carbon material is obtained. After the carbonization, some metal simple substances and metal compounds mainly remain in the porous carbon material, and in this embodiment, the metal simple substances and metal compounds are mainly removed by acid washing. In one embodiment, the acid is one of sulfuric acid and hydrochloric acid, and the acid concentration is 0.5-3 mol/L. And after the acid washing is finished, washing the polymer material after the acid washing for 3-5 times by using deionized water so as to remove the residual acid of the metal simple substance and the metal compound.
In a specific embodiment, after the porous carbon material is washed by acid and deionized water, the porous carbon material is subjected to forced air drying to obtain the carbon-based nitrogen reduction catalyst. In a specific embodiment, the air-blast drying temperature is 50-100 ℃, and the air-blast drying time is 6-24 hours, so that the carbon-based nitrogen reduction catalyst with high graphitization degree and high specific surface area is obtained.
In a specific embodiment, the invention further provides an application of the porous carbon-based nitrogen reduction catalyst, and the porous carbon-based nitrogen reduction catalyst prepared by the preparation method is used for synthesizing ammonia by electrocatalysis of nitrogen.
In a specific embodiment, the porous carbon-based nitrogen reduction catalyst obtained by the preparation method is mixed with an absolute ethyl alcohol dispersant in a 10ml strain bottle, then ultrasonic treatment is carried out for 30min, and 50 mul of film-forming agent Nafion is added for ultrasonic treatment for 20min to obtain the porous carbon-based nitrogen reduction catalyst suspension. Then, 10 mul of proportionally prepared porous carbon-based nitrogen reduction catalyst suspension is measured by a pipette and evenly dripped on a cutting area of 1 x 1cm-2And baking the commercial carbon cloth for 1-2 min by using an infrared lamp. Na was used at a concentration of 0.05M2SO4The solution is used as electrolyte to prepare a three-electrode system. The linear sweep voltammetry curve is tested under the conditions that the potential window is 0.4 to-0.8V and the sweep speed is 5 mV/s.
In one embodiment, ammonium chloride is used as a standard reagent in the present example at 0.05M Na2SO4Ammonium chloride standard solutions of 0, 0.25, 0.5 and 1 mu g/ml are prepared in the solution respectively and are subjected to chromogenic reaction to test the absorbance. Taking 2ml of standard solution, adding 2ml of 1mol/L sodium hydroxide solution (containing 5 wt% of salicylic acid and 5 wt% of sodium citrate dihydrate), then adding 1ml of 0.05mol/L sodium hypochlorite solution, finally adding 0.2ml of 5 wt% sodium nitroprusside dihydrate solution, standing and developing for 2 hours at room temperature in a dark condition, performing spectral scanning in a wavelength range of 550-750 nm by using an ultraviolet visible spectrophotometer, recording an absorbance value at 655nm, and drawing a standard curve with the concentration.
Further, after the standard curve is obtained, the porous carbon-based nitrogen reduction catalyst obtained in this example is usedAnd 2ml of electrolyte after the electrolyte is used for 2 hours, adding 2ml of 1mol/L sodium hydroxide solution (containing 5 wt% of salicylic acid and 5 wt% of sodium citrate dihydrate), then adding 1mol of 0.05mol/L sodium hypochlorite solution, finally adding 0.2ml of 5 wt% sodium nitroprusside dihydrate, standing and developing for 2 hours at room temperature in a dark place, performing spectral scanning within the wavelength range of 550-750 nm by using an ultraviolet visible spectrophotometer, recording the absorbance value at 655nm, and combining with a standard curve to finally obtain the concentration of ammonia. After data processing and calculation, the ammonia production rate and Faraday efficiency of the electro-catalysis ammonia production are obtained, and the calculated ammonia production rate can reach 26ugNH3h-1mg-1 catAnd the Faraday efficiency is 9 percent, which shows that the porous carbon-based nitrogen reduction catalyst prepared by the invention has high nitrogen reduction capability.
The invention takes macromolecules containing glucose units as raw materials, and the macromolecules are coordinated and anchored with transition metals to form monoatomic atoms, so as to obtain multiple active centers; roasting and carbonizing the pore-forming agent to obtain the porous carbon-based nitrogen reduction catalyst with high specific surface area, enhancing the nitrogen reduction performance of the carbon material non-noble metal catalyst, and realizing the preparation of the nitrogen reduction catalyst with low cost and high catalytic activity under the conditions of mildness, safety and environmental protection.
The invention is further illustrated by the following specific examples.
Example 1
The preparation method of the chitin porous carbon-based nitrogen reduction catalyst comprises the following steps:
(1) putting 3g of commercial chitin in a porcelain boat, pre-oxidizing for 2h at 250 ℃ in the air atmosphere, and after the reaction is finished, cooling the reaction system to room temperature to obtain a pre-oxidized chitin-based carbon material;
(2) according to ZnCl2、CoCl3And the preoxidized chitin-based carbon material is prepared by mixing the following components in a mass ratio of 1: 3: 1 in a ratio of N2Heating to 800 ℃ at a heating rate of 5 ℃/min in the atmosphere, and keeping the temperature for 2 hours to obtain a carbonized chitin-based carbon material;
(3) when the mixture is cooled to room temperature, removing Co and Zn metal compounds in the chitin-based porous carbon by using HCl with the concentration of 2M, washing the mixture for 5 times by using deionized water, and drying the mixture to obtain the chitin-based porous nitrogen reduction catalyst;
testing the performance of the chitin porous carbon-based nitrogen reduction catalyst:
(4) mixing a chitin porous carbon-based nitrogen reduction catalyst and an absolute ethyl alcohol dispersant in a 10ml strain bottle, performing ultrasonic treatment for 30min, and adding 50 mul of a film-forming agent Nafion, and performing ultrasonic treatment for 20min to obtain a nitrogen reduction catalyst suspension;
(5) measuring 10 mul of proportionally prepared nitrogen reduction catalyst suspension by using a pipette, and uniformly dripping the nitrogen reduction catalyst suspension on a cutting area of 1 x 1cm-2Baking the commercial carbon cloth for 1-2 min by using an infrared lamp, wherein Na with the concentration of 0.05M is used2SO4The solution is used as electrolyte to prepare a three-electrode system. The linear sweep voltammetry curve of the prepared chitin porous carbon-based nitrogen reduction catalyst is tested under the conditions that the potential window is 0.4 to-0.8V and the sweep speed is 5 mV/s.
(6) Taking 2ml of electrolyte after the chitin porous carbon-based nitrogen reduction catalyst operates for 2 hours, adding 2ml of 1mol/L sodium hydroxide solution (containing 5 wt% of salicylic acid and 5 wt% of sodium citrate dihydrate), then adding 1ml of 0.05mol/L sodium hypochlorite solution, finally adding 0.2ml of 5 wt% sodium nitroprusside dihydrate, standing and developing for 2 hours at room temperature in a dark place, performing spectral scanning within a wavelength range of 550-750 nm by using an ultraviolet visible spectrophotometer, recording an absorbance value at 655nm, and combining with a working curve to finally obtain the concentration of ammonia. And obtaining the ammonia production rate and Faraday efficiency of the electro-catalysis ammonia production after data processing and calculation.
Example 2
The preparation method and the performance test of the cyclodextrin porous carbon-based nitrogen reduction catalyst are as follows:
(1) weighing 2g of beta-cyclodextrin and 120ml of deionized water, mixing and stirring, placing the mixture in a 50ml of polytetrafluoroethylene lining for hydrothermal pretreatment, treating the mixture at the hydrothermal temperature of 220 ℃ for 6 hours, and after the reaction is finished, cooling the temperature of a reaction system to room temperature to obtain a pretreated cyclodextrin-based carbon material;
(2) according to CoCl3And the mass ratio of the pretreated cyclodextrin-based carbon material to the pretreated cyclodextrin-based carbon material is 1:1 in a ratio of N2Heating at a heating rate of 5 deg.C/min under atmosphereKeeping the temperature at 800 ℃ for 2h to obtain a carbonized cyclodextrin-based carbon material;
(3) when the catalyst is cooled to room temperature, removing metal compounds in the cyclodextrin-based carbon material by using HCl with the concentration of 2M, washing the catalyst for 5 times by using deionized water, and drying the catalyst to obtain the cyclodextrin porous carbon-based nitrogen reduction catalyst;
and (3) testing the performance of the cyclodextrin porous carbon-based nitrogen reduction catalyst:
(4) mixing a cyclodextrin-based carbon material and an absolute ethyl alcohol dispersant in a 10ml strain bottle, performing ultrasonic treatment for 30min, and adding 50 mu l of a film-forming agent Nafion, and performing ultrasonic treatment for 20min to obtain a nitrogen reduction catalyst suspension;
(5) measuring 10 mul of proportionally prepared nitrogen reduction catalyst suspension by using a pipette, and uniformly dripping the nitrogen reduction catalyst suspension on a cutting area of 1 x 1cm-2Baking the commercial carbon cloth for 1-2 min by using an infrared lamp, wherein Na with the concentration of 0.05M is used2SO4The solution is used as electrolyte to prepare a three-electrode system. And testing the linear sweep voltammetry curve of the prepared cyclodextrin porous carbon-based nitrogen reduction catalyst under the conditions that the potential window is 0.4 to-0.8V and the sweep speed is 5 mV/s.
(6) Taking 2ml of electrolyte after the cyclodextrin porous carbon-based nitrogen reduction catalyst operates for 2 hours, adding 2ml of 1mol/L sodium hydroxide solution (containing 5 wt% of salicylic acid and 5 wt% of sodium citrate dihydrate), then adding 1ml of 0.05mol/L sodium hypochlorite solution, finally adding 0.2ml of 5 wt% sodium nitroprusside dihydrate, standing and developing for 2 hours at room temperature in a dark place, performing spectral scanning within a wavelength range of 550-750 nm by using an ultraviolet visible spectrophotometer, recording an absorbance value at 655nm, and combining with a working curve to finally obtain the concentration of ammonia. And obtaining the ammonia production rate and Faraday efficiency of the electro-catalysis ammonia production after data processing and calculation.
Fig. 1 and 3 are scanning electron micrographs of the chitin porous carbon-based nitrogen reduction catalyst and the cyclodextrin porous carbon-based nitrogen reduction catalyst prepared in examples 1 and 2, respectively, and it can be seen from fig. 1 that the chitin porous carbon-based nitrogen reduction catalyst after adding the pore-forming agent contains a large number of micropores and mesopores; it can be seen from fig. 3 that the cyclodextrin porous carbon-based nitrogen reduction catalyst prepared in example 2 is in the form of carbon spheres, but since no pore-forming agent is added, it cannot be seen that the cyclodextrin porous carbon-based nitrogen reduction catalyst has micropores and mesopores.
Fig. 2 and 4 are linear sweep voltammograms of the chitin porous carbon-based nitrogen reduction catalyst and the cyclodextrin porous carbon-based nitrogen reduction catalyst prepared in example 1 and example 2, respectively, in a nitrogen gas and argon gas atmosphere. FIG. 5 is a linear sweep voltammogram of a commercial Pt/C catalyst under nitrogen and argon atmosphere. As can be seen from fig. 2, 4 and 5, the prepared chitin porous carbon-based nitrogen reduction catalyst and cyclodextrin porous carbon-based nitrogen reduction catalyst have larger initial potential and limiting current density under nitrogen and argon atmosphere compared with the existing commercial Pt/C catalyst. However, the initial potential and the limiting current density of the chitin porous carbon-based nitrogen reduction catalyst are better than those of the cyclodextrin porous carbon-based nitrogen reduction catalyst due to the addition of the pore-forming agent during preparation.
FIG. 6 is a 0.05M solution of Na in ammonium chloride as a standard reagent2SO4Preparing ammonium chloride standard solutions of 0, 0.25, 0.5 and 1 mu g/ml in the solution respectively, and testing ultraviolet spectrograms after color reaction. FIG. 7 is a standard curve obtained by plotting the absorbance at 655nm against the concentration of 0, 0.25, 0.5, 1. mu.g/ml standard solutions of ammonium chloride after color reaction.
Fig. 8 is an ultraviolet spectrum of the electrolyte after the electrolyte color development after the chitin porous carbon-based nitrogen reduction catalyst and the cyclodextrin porous carbon-based nitrogen reduction catalyst prepared in examples 1 and 2 and the commercial Pt/C catalyst run for 2 hours. Fig. 9 shows ammonia production rates and faraday efficiencies of the chitin porous carbon-based nitrogen reduction catalyst and cyclodextrin porous carbon-based nitrogen reduction catalyst prepared in examples 1 and 2, and the commercial Pt/C catalyst. As can be seen from fig. 9, it is calculated that the chitin porous carbon-based nitrogen reduction catalysts and cyclodextrin porous carbon-based nitrogen reduction catalysts prepared in examples 1 and 2 have higher ammonia production rates and faraday efficiencies than commercial Pt/C catalysts. Wherein, the ammonia generating rate of the chitin porous carbon-based nitrogen reduction catalyst can reach 26ug due to the addition of the pore-forming agentNH3h-1mg-1 catThe Faraday efficiency was 9%.
In summary, the invention discloses a preparation method and application of a porous carbon-based nitrogen reduction catalyst, wherein the preparation method comprises the steps of pretreating a high polymer raw material containing glucose units to obtain a pretreated high polymer material; mixing the pretreated high polymer material with a pore-forming agent and a catalyst, and carbonizing under the protection of inert gas to obtain a porous carbon material; and washing the porous carbon material with acid and deionized water in sequence, and then carrying out forced air drying to obtain the carbon-based nitrogen reduction catalyst. The invention takes macromolecules containing glucose units as raw materials, and the macromolecules are coordinated and anchored with transition metals to form monoatomic atoms, so as to obtain multiple active centers; roasting and carbonizing the pore-forming agent to obtain the porous carbon-based nitrogen reduction catalyst with high specific surface area, enhancing the nitrogen reduction performance of the carbon material non-noble metal catalyst, and realizing the preparation of the nitrogen reduction catalyst with low cost and high catalytic activity under the conditions of mildness, safety and environmental protection.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a porous carbon-based nitrogen reduction catalyst is characterized by comprising the following steps:
pretreating a high polymer raw material containing a glucose unit to obtain a pretreated high polymer material;
mixing the pretreated high polymer material with a pore-forming agent and a catalyst, and carbonizing under the protection of inert gas to obtain a porous carbon material;
and washing the porous carbon material with acid and deionized water in sequence, and then carrying out forced air drying to obtain the carbon-based nitrogen reduction catalyst.
2. The method for preparing the porous carbon-based nitrogen reduction catalyst according to claim 1, wherein the step of pretreating a polymer raw material containing glucose units to obtain a pretreated polymer material comprises:
and carrying out hydrothermal pretreatment on the high polymer raw material containing the glucose unit at 200-220 ℃ for 5-6 h to obtain a pretreated high polymer material.
3. The method for preparing the porous carbon-based nitrogen reduction catalyst according to claim 1, wherein the step of pretreating a polymer raw material containing glucose units to obtain a pretreated polymer material comprises:
pre-oxidizing the high polymer raw material containing the glucose unit for 1-5 hours at 200-300 ℃ to obtain a pretreated high polymer material.
4. The method of claim 1, wherein the pore former is one of zinc chloride and potassium hydroxide.
5. The method of preparing a porous carbon-based nitrogen reduction catalyst according to claim 1, wherein the catalyst is an inorganic salt of a transition metal.
6. The preparation method of the porous carbon-based nitrogen reduction catalyst according to claim 1, wherein the mass ratio of the pretreated polymer material, the pore-forming agent and the catalyst is 1:1: 1-1: 5: 5.
7. The preparation method of the porous carbon-based nitrogen reduction catalyst according to claim 1, wherein the carbonization temperature is 600-900 ℃; the carbonization time is 1-3 h; and the temperature rise rate during carbonization is 2-5 ℃/min.
8. The method of claim 1, wherein the acid is one of sulfuric acid and hydrochloric acid; the concentration of the acid is 0.5-3 mol/L.
9. The preparation method of the porous carbon-based nitrogen reduction catalyst according to claim 1, wherein the forced air drying temperature is 50-100 ℃; and the air blast drying time is 6-24 h.
10. The application of the porous carbon-based nitrogen reduction catalyst is characterized in that the porous carbon-based nitrogen reduction catalyst prepared by the preparation method of any one of claims 1 to 9 is used for synthesizing ammonia by electrocatalysis of nitrogen.
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