CN114702024B - Preparation method and application of doped carbon aerogel - Google Patents
Preparation method and application of doped carbon aerogel Download PDFInfo
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- CN114702024B CN114702024B CN202210356784.6A CN202210356784A CN114702024B CN 114702024 B CN114702024 B CN 114702024B CN 202210356784 A CN202210356784 A CN 202210356784A CN 114702024 B CN114702024 B CN 114702024B
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- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000017 hydrogel Substances 0.000 claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 55
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 33
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004202 carbamide Substances 0.000 claims abstract description 31
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 230000009467 reduction Effects 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 239000004964 aerogel Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000004108 freeze drying Methods 0.000 claims abstract description 11
- 229920000875 Dissolving pulp Polymers 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 229920002678 cellulose Polymers 0.000 claims description 25
- 239000001913 cellulose Substances 0.000 claims description 25
- 235000010980 cellulose Nutrition 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000012266 salt solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229920003086 cellulose ether Polymers 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000002019 doping agent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- RFRMMZAKBNXNHE-UHFFFAOYSA-N 6-[4,6-dihydroxy-5-(2-hydroxyethoxy)-2-(hydroxymethyl)oxan-3-yl]oxy-2-(hydroxymethyl)-5-(2-hydroxypropoxy)oxane-3,4-diol Chemical compound CC(O)COC1C(O)C(O)C(CO)OC1OC1C(O)C(OCCO)C(O)OC1CO RFRMMZAKBNXNHE-UHFFFAOYSA-N 0.000 claims 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 229920000557 Nafion® Polymers 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000005868 electrolysis reaction Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 4
- 239000008108 microcrystalline cellulose Substances 0.000 description 4
- 229940016286 microcrystalline cellulose Drugs 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- 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
- C25B1/01—Products
- C25B1/23—Carbon monoxide or syngas
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to CO 2 The technical field of electrocatalytic reduction, in particular discloses a preparation method and application of doped carbon aerogel, wherein the method comprises the following steps: s1, dissolving cellulose or a derivative thereof in a urea alkali solution to obtain a precursor solution, wherein the urea alkali solution is urea aqueous solution containing sodium hydroxide and potassium hydroxide; s2, preparing doped hydrogel, wherein the doped hydrogel is non-metal doped hydrogel or metal doped hydrogel; s3, freeze-drying the doped hydrogel to obtain doped aerogel; s4, carbonizing the doped aerogel at high temperature to obtain the doped carbon aerogel. The doped carbon aerogel prepared by the method has large specific surface area, rich pore structure, good conductivity and stability, and the doped carbon aerogel is used as a carbon dioxide electro-reduction catalyst, has high catalytic activity and good stability, and is suitable for large-scale popularization and use.
Description
Technical Field
The invention belongs to CO 2 The technical field of electrocatalytic reduction, and more particularly relates to a preparation method and application of doped carbon aerogel.
Background
At present, the concentration of carbon dioxide in the atmosphere exceeds the standard, so that serious greenhouse effect is caused, and if no effective regulation and control means are available, 500ppm can be expected by 2050, and ecological civilization of the world is threatened. If an effective method can be found to convert carbon dioxide into high value added fuels such as methane or alcohols, this can both slow down the greenhouse effect and address a portion of the energy crisis. The common carbon dioxide conversion utilization mode at present is thermocatalytic conversion, photocatalytic conversion and electrocatalytic conversion. However, for thermocatalytic conversion, carbon dioxide is a nonpolar linear molecule, its thermodynamic properties are extremely stable, and the cleavage of the c=o bond requires overcoming a large energy barrier, and a large driving force must be provided to the reaction system during the conversion. The photocatalytic conversion may be driven by inexpensive and readily available solar energy, but the catalyst is also subject to the potential for photo-corrosion. Compared with other conversion modes, the electrocatalytic technology has stronger controllability, and the whole process can not generate extra carbon dioxide gas, so that the problem of greenhouse effect can be solved from the source.
For electrocatalytic reduction of carbon dioxide, the preparation of a highly efficient catalyst is important. It is well known that noble metals (e.g., au, ag) and their alloys are highly effective as CO 2 The catalysts are reduced because they have excellent activity and selectivity. However, the high cost and scarcity of these precious metals have prevented their large-scale use. It is a long-felt goal to develop efficient, inexpensive and stable catalysts with low noble metal loading or no noble metal material.
The carbon-based catalyst is focused by a plurality of researchers due to the advantages of wide sources, low preparation cost, good conductivity, contribution to industrial application and the like, and is widely applied to hydrogen evolution reaction, oxygen reduction reaction and electrocatalytic reduction of CO 2 Reactions, etc., are among the most promising electrocatalysts. However, the pure carbon material does not have a catalytic active site, and needs to be modified to improve the catalytic performance. The loading of metal ions on carbon-based materials helps to improve the catalytic activity, but the active sites of the metal ions directly loaded on the carbon-based catalysts are easy to fall off at present, thereby leading to the stability thereofPoor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method and application of doped carbon aerogel, and aims to solve the problems of low catalytic activity, poor stability and difficult large-scale use of the existing electrochemical catalyst material.
In order to achieve the above object, the present invention provides a method for preparing a doped carbon aerogel, comprising the steps of:
s1, dissolving cellulose or a derivative thereof in a urea alkali solution to obtain a precursor solution, wherein the urea alkali solution is urea aqueous solution containing sodium hydroxide and potassium hydroxide;
s2, preparing doped hydrogel which is non-metal doped hydrogel or metal doped hydrogel, wherein the non-metal doped hydrogel is obtained by adding a non-metal doping reagent and a cross-linking agent into the precursor solution, stirring and standing, and the metal doped hydrogel is obtained by adding the cross-linking agent into the precursor solution, stirring and standing or is obtained by soaking the non-metal doped hydrogel in a metal salt solution;
s3, freeze-drying the doped hydrogel to obtain doped aerogel;
s4, carbonizing the doped aerogel at high temperature to obtain the doped carbon aerogel.
Preferably, in the step S1, the mass ratio of the cellulose or the derivative thereof, the potassium hydroxide, the sodium hydroxide, the urea and the water in the precursor solution is 5 (1-2)/(3-8)/(10-15)/(80-100).
Preferably, in the step S1, the urea alkali solution is pre-cooled to the temperature of minus 20 ℃ to minus 10 ℃, and then the cellulose or the derivative thereof is immediately added and stirred, so that the cellulose or the derivative thereof is completely dissolved.
Preferably, in step S1, the cellulose or the derivative thereof is one or more of a poly-polymerized cellulose, a cellulose ether, a methyl cellulose, a hydroxypropyl methyl cellulose, a hydroxyethyl cellulose and a carboxymethyl cellulose.
Preferably, in step S2, the doped hydrogel prepared is a metal doped hydrogel.
Further preferably, the metal-doped hydrogel is obtained by immersing the non-metal-doped hydrogel in a metal salt solution.
Preferably, in step S2, the non-metal doping agent is one or more of boric acid, phosphoric acid, melamine, polyaniline and polypyrrole.
Preferably, in step S2, the metal salt solution is FeCl 3 、NiCl 2 、CoCl 2 、Cu(NO 3 ) 2 、CuCl 2 、ZnCl 2 And Zn (NO) 3 ) 2 The time for soaking the metal salt solution in the metal salt solution is 18-30 h.
Preferably, in the step S3, the pre-cooling temperature of freeze drying is-40 ℃ to-60 ℃ and the drying time is 36h to 72h.
Preferably, in step S4, the conditions of the high-temperature carbonization process are: and heating to 650-950 ℃ at a heating rate of 5-10 ℃ per minute, and preserving heat for 0.5-2 hours.
According to another aspect of the present invention, there is also provided the use of a doped carbon aerogel in the electrocatalytic reduction of carbon dioxide, the catalyst employed in the electrocatalytic reduction of carbon dioxide comprising the doped carbon aerogel prepared by the above method.
Preferably, the preparation method of the catalyst comprises the following steps: and dissolving the doped carbon aerogel in a mixed solution of deionized water, ethanol and Nafion film solution, performing ultrasonic dispersion, and uniformly coating the obtained solution on carbon paper to obtain the catalyst.
In general, the above technical solutions conceived by the present invention have the following beneficial effects compared with the prior art:
(1) The doped carbon aerogel is prepared by taking cellulose as a precursor through a sol-gel method, heteroatom impregnation and one-step pyrolysis, not only maintains the characteristics of large specific surface area and rich pore structure of a carbon-based material, but also has good catalytic activity and stability, and provides a new idea for improving the electrocatalytic reduction reaction activity of carbon dioxide. When nonmetal doping is carried out, the introduction of nonmetal heteroatoms can lead to uneven electron cloud distribution on chemical bonds or increase defect sites on the carbon-based porous material, and provide more reactive sites for catalytic reaction, thereby improving the activity of the catalyst; when the metal is doped, the metal is firstly carried on the aerogel in a dispersing way by an impregnation method, and then carbonized together, so that metal ions can be better attached on the carbon aerogel, and the influence on the catalytic activity caused by falling of active sites in the catalytic reaction process is avoided.
(2) The invention uses the carbon-based material with special porous structure to load different metals to change the selectivity of the catalyst to the carbon dioxide reduction product, and CO is a key raw material for producing liquid fuel through a mature industrial process.
(3) The doped carbon aerogel disclosed by the invention does not need to introduce noble metal materials, can achieve a good and stable catalytic carbon dioxide reduction effect, and is low in preparation cost and higher in economical efficiency.
(4) The invention uses the cellulose-based carbon aerogel with a three-dimensional network pore structure as a carrier, can provide sufficient reaction channels for catalytic reaction, can further improve catalytic activity through metal and/or nonmetal doping, has simple preparation process, low-cost and environment-friendly cellulose raw materials, has high application value in the field of carbon dioxide electrocatalytic reduction, and is suitable for industrial application.
Drawings
FIG. 1 is a process flow diagram for preparing a doped carbon aerogel according to an embodiment of the present invention.
FIG. 2 shows Zn preparation at various carbonization temperatures according to example 1 of the present invention 2+ Carbon doped aerogel catalyst at 0.1M KHCO 3 LSV curve in electrolyte.
FIG. 3 shows a catalyst Zn prepared in example 1 of the present invention 2+ -750 faraday efficiencies for each product at different potentials.
FIG. 4 shows an embodiment of the present invention1 catalyst Zn prepared in the following manner 2+ -750 stability test results for 8h of continuous electrolysis.
FIG. 5 shows a nitrogen-doped carbon aerogel catalyst prepared at various carbonization temperatures in accordance with example 2 of the present invention at 0.1M KHCO 3 LSV curve in electrolyte.
FIG. 6 shows the Faraday efficiencies of the respective products at different potentials for catalysts N3-750 prepared in example 2 of the present invention.
FIG. 7 shows the stability test results of the catalyst N3-750 prepared in example 2 of the present invention for electrolysis for 8 hours.
FIG. 8 shows a Zn-N co-doped carbon aerogel catalyst prepared at various carbonization temperatures in accordance with example 3 of the present invention at 0.1M KHCO 3 LSV curve in electrolyte.
FIG. 9 shows a catalyst Zn prepared in example 3 of the invention 2+ +N-850 Faraday efficiency of each product at different potentials.
FIG. 10 shows a catalyst Zn prepared in example 3 of the invention 2+ Stability test results for continuous electrolysis for 8h with +N-850.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Referring to fig. 1, the preparation method of the doped carbon aerogel provided by the invention comprises the following steps:
s1, dissolving cellulose and derivatives thereof in urea alkali solution to obtain a precursor solution, wherein the urea alkali solution is urea aqueous solution containing sodium hydroxide and potassium hydroxide;
s2, preparing doped hydrogel, wherein the doped hydrogel is non-metal doped hydrogel or metal doped hydrogel, the non-metal doped hydrogel is obtained by adding a non-metal doping reagent and a cross-linking agent into the precursor solution, stirring and standing, and the metal doped hydrogel is obtained by adding a cross-linking agent into the precursor solution, stirring and standing or soaking the non-metal doped hydrogel in a metal salt solution;
s3, freeze-drying the doped hydrogel to obtain doped aerogel;
s4, carbonizing the doped aerogel at high temperature to obtain the doped carbon aerogel.
In the step S1 of some embodiments, the mass ratio of potassium hydroxide, sodium hydroxide, urea and water in the urea alkali solution is (1-2)/(3-8)/(10-15)/(80-100). The KOH is added into the urea alkali solution in a certain proportion, and because the KOH has an activating effect, a series of physical and chemical changes can occur between KOH and C and between a product and C in the pyrolysis carbonization process of the aerogel, and the activating and pore-forming process of the carbon aerogel is completed, so that the pore structure of the carbon aerogel is more abundant. At the same time, however, the alkali in the urea alkali solution cannot be completely replaced by potassium hydroxide, i.e. a certain proportion of sodium hydroxide is also required in the urea alkali solution, otherwise the gel cannot be successfully formed in step S2.
In some embodiments, the urea alkali solution is pre-cooled to-20 ℃ to-10 ℃ and then immediately added with the cellulose or the derivative thereof for stirring, so that the urea alkali solution is pre-cooled to a certain low temperature and then rapidly added with the cellulose for a period of time, and the cellulose is completely dissolved to form a transparent solution, so that uniform hydrogel can be prepared later. In particular, the cellulose and its derivatives may be one or more of a poly-polymerized cellulose, a cellulose ether, a methyl cellulose, a hydroxypropyl methyl cellulose, a hydroxyethyl cellulose and a carboxymethyl cellulose. The mass ratio of cellulose or the derivative thereof, potassium hydroxide, sodium hydroxide, urea and water in the transparent precursor solution is 5 (1-2)/(3-8)/(10-15)/(80-100).
The carbon aerogel provided by the invention comprises three doping types: the non-metal doping, metal doping and metal/non-metal co-doping correspond to the step S2 in which the doped hydrogel is a non-metal doped hydrogel or a metal doped hydrogel, wherein the metal doped hydrogel includes two metal doped hydrogels and a metal/non-metal doped hydrogel.
The specific method for preparing the nonmetallic doped hydrogel comprises the following steps: and (2) adding a non-metal doping reagent and a cross-linking agent into the precursor solution prepared in the step (S1), uniformly stirring, and standing to obtain the non-metal doped hydrogel, wherein the non-metal doping reagent is one or more of boric acid, phosphoric acid, melamine, polyaniline and polypyrrole and is used for boron doping, phosphorus doping or nitrogen doping. Preferably, the mass ratio of cellulose or a derivative thereof to the nonmetallic doping agent in the precursor solution is (2-5): 1.
The specific method for preparing the metal doped hydrogel comprises the following steps: adding a cross-linking agent into the precursor solution, stirring to enable the cross-linking agent to undergo a gel reaction, standing to obtain hydrogel, and soaking the hydrogel in a metal salt solution for a period of time to obtain the metal doped hydrogel.
The specific method for preparing the metal/nonmetal co-doped hydrogel comprises the following steps: and (3) placing the prepared nonmetallic doped hydrogel into a metal salt solution for soaking for a period of time to obtain the metallic/nonmetallic codoped hydrogel.
In the metal doping process, the metal salt solution used can be FeCl 3 、NiCl 2 、CoCl 2 、Cu(NO 3 ) 2 、CuCl 2 、ZnCl 2 And Zn (NO) 3 ) 2 The concentration of the metal salt solution is 0.5mol/L to 1mol/L, and the time for soaking the hydrogel is 18h to 30h, so that the metal hetero atoms are fully attached to the hydrogel. Cl in Metal salt solution - Is favorable for inhibiting the occurrence of hydrogen evolution reaction in the electrocatalytic reduction process of carbon dioxide.
The crosslinking agent used in this embodiment may be any type of liquid crosslinking agent used for crosslinking to form a gel, such as epichlorohydrin, dicumyl peroxide, benzoyl peroxide, and the like. The adding ratio of the cross-linking agent to cellulose or derivatives thereof, potassium hydroxide, sodium hydroxide, urea and water in the precursor solution is 9mL, 5g (1-2 g), 3-8 g (10-15 g) and 80-100 g.
In step S3 of some embodiments, the pre-cooling temperature of freeze drying is-40 ℃ to-60 ℃ and the drying time is 36h to 72h.
In step S4 of some embodiments, the conditions of the high temperature carbonization process are: and heating to 650-950 ℃ at a heating rate of 5-10 ℃ per minute, and preserving heat for 0.5-2 hours. Further preferably, the carbonization temperature is 750 ℃ to 850 ℃.
On the other hand, the invention also provides application of the doped carbon aerogel in the electrocatalytic reduction of carbon dioxide, and the catalyst used in the electrocatalytic reduction of carbon dioxide can comprise the prepared doped carbon aerogel. Specifically, the preparation method of the catalyst comprises the following steps: and dissolving the doped carbon aerogel in a mixed solution of deionized water, ethanol and Nafion film solution, performing ultrasonic dispersion, and uniformly coating the obtained solution on carbon paper to obtain the catalyst. Preferably, the volume ratio of deionized water, ethanol and Nafion film solution is 4:26:70, and the specification of the carbon paper is 1cm multiplied by 2cm.
Preferably, the prepared metal/nonmetal doped carbon aerogel is prepared into a catalyst for electrocatalytic reduction of carbon dioxide, so that the catalytic activity can be remarkably improved, and meanwhile, the catalyst has better selectivity for specific reduction products (such as CO).
The following describes the above technical scheme in detail with reference to specific embodiments.
Example 1
This example prepared a Zn 2+ The specific operation steps of the carbon-doped aerogel catalyst are as follows:
mixing 1g of potassium hydroxide, 6g of sodium hydroxide, 12g of urea and 81g of deionized water, uniformly stirring, and then placing in a refrigerator at the temperature of minus 18 ℃ for freezing for 2 hours; dissolving 5g of microcrystalline cellulose in the thawed urea alkali solution, and magnetically stirring for 2 hours to uniformly dissolve the microcrystalline cellulose; adding 9mL of epichlorohydrin into the cellulose solution and uniformly stirring; standing the mixed solution for 4 hours at normal temperature to obtain hydrogel; 6.816g ZnCl is taken 2 Dissolving in 100mL deionized water, and soaking the hydrogel in the deionized water for 24h; will be soaked with Zn 2+ The hydrogel of the salt solution is put into a freeze dryer, precooled for 5 hours at the temperature of minus 55 ℃, and then dried for 48 hours in vacuum to obtain cellulose-based aerogel; placing the same four aerogels into a tube furnace, respectively heating to 650 ℃, 750 ℃, 850 ℃, 950 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to obtainUp to four kinds of Zn 2+ Doping carbon aerogel; grinding each obtained carbon aerogel into powder, dissolving in deionized water, ethanol and Nafion film solution for 0.5h by ultrasonic treatment, wherein the volume ratio of the deionized water to the ethanol to the Nafion film solution is 40:260:700 to obtain ink-like liquid, and coating the ink-like liquid on carbon paper with the volume of 1cm multiplied by 2cm to obtain available catalysts, namely Zn respectively 2+ -650、Zn 2+ -750、Zn 2+ -850 and Zn 2+ -950。
Electrochemical performance test was performed using an electrochemical workstation CHI660E using a three electrode system in which a platinum sheet was used as a counter electrode, ag/AgCl (saturated KCl) was used as a reference electrode, and the 4 catalysts prepared in this example and pure carbon paper were respectively sandwiched between electrode clamps as working electrodes, and a typical H-type cell was selected as the cell, and a proton exchange membrane (Nafion 177) washed with ultra-pure water was placed between the cathode and anode compartments of the cell to ensure that only hydrogen ions were allowed to pass. After H-type electrolytic cells are assembled respectively, 50mL of 0.1mol/L KHCO prepared by ultrapure water is added into a cathode chamber and an anode chamber of the electrolytic cell 3 The solution is sealed, high-purity nitrogen with the flow rate of 25sccm is controlled to be introduced into a cathode chamber by a rotameter under the condition of room temperature, then high-purity carbon dioxide with the flow rate and time identical to those of the prior solution is introduced, the electrolytic reaction is carried out at different potentials, the flow rate of the carbon dioxide is controlled to be constant at 25sccm during the electrolytic reaction, and gas generated by the reaction is synchronously introduced into a gas chromatograph for carrying out online analysis on the gas components and the content, and the gas is tested once every 1 h.
As can be seen from fig. 2, the catalyst (Zn 2+ -T) the limiting current density is far greater than that of pure carbon paper and can reach-27.78 mA cm at most -2 And the initial potential is at least-0.518V vs. RHE, which indicates the load of Zn 2+ The carbon aerogel catalyst has stronger electrocatalytic activity. FIG. 3 shows catalyst Zn 2+ The faraday efficiencies of the different products at different potentials of-750 can be seen to be up to 77.89% for the CO product at-1.0V potential. FIG. 4 shows catalyst Zn 2+ -750 current density and CO after 8h of continuous electrolysis 2 Trend of change in Faraday efficiency of reduction product, fromThe graph shows that after 8 hours of electrolysis, the current density is slightly reduced, the Faraday efficiency of CO is not obviously changed, and the Faraday efficiency is only reduced from 77.89% to 74.26%; CH (CH) 4 The faraday efficiency of (c) decreases from 4.18% to 2.66%. The results show that the catalyst has excellent stability.
Example 2
The nitrogen-doped carbon aerogel catalyst is prepared by the embodiment, and the specific operation steps are as follows:
1g of potassium hydroxide, 6g of sodium hydroxide and 12g of urea are dissolved in 81g of deionized water and stirred uniformly, and the mixture is put into a refrigerator for freezing, and the precooling time is 2 hours, and the temperature is minus 12 ℃; taking out the pre-cooled solution, thawing to a non-ice state at room temperature, adding 5g of microcrystalline cellulose, and magnetically stirring for 2.5h; 9mL of epichlorohydrin and 1.4g of melamine are added, the magnetic stirring is carried out for 2.5 hours, the magnetons are taken out, and the mixture is left at room temperature for 4 hours until hydrogel is formed; washing the hydrogel with deionized water for about 10 times to neutrality, putting the hydrogel into a freeze dryer for freeze drying, firstly putting the hydrogel into a cold well for precooling for 6 hours at the temperature of minus 55 ℃, then transferring the sample into a vacuum drying chamber, and obtaining the nitrogen-doped cellulose-based aerogel after the freeze drying time is 48 hours; placing the same four aerogels into a tube furnace, respectively heating to 650 ℃, 750 ℃, 850 ℃, 950 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to obtain four nitrogen-doped carbon aerogels; and grinding each obtained carbon aerogel into powder, dissolving the powder in deionized water, ethanol and Nafion film solution for ultrasonic treatment for 0.5h, wherein the volume ratio of the deionized water to the ethanol to the Nafion film solution is 40:260:700, obtaining ink-like liquid, and coating the ink-like liquid on carbon paper with the volume of 1cm multiplied by 2cm to obtain available catalysts of N3-650, N3-750, N3-850 and N3-950.
The electrolytic cell was assembled with reference to example 1, and the catalyst prepared in this example was tested for its ability to electrocatalytically reduce carbon dioxide. As can be seen from FIG. 5, the limiting current density of the catalyst (N-T) prepared at different carbonization temperatures is far greater than that of pure carbon paper, and can reach-27.25 mA cm at most -2 And the initial potential is at least-0.425V vs. RHE, which shows that the nitrogen-doped carbon aerogel catalyst has stronger electrocatalytic activity. FIG. 6 shows the catalyst N3-750 at different powersThe Faraday efficiencies of the different products in the position can be seen to be 75.9% for the CO product at-1.0V potential. FIG. 7 shows the current density and CO after 8h of continuous electrolysis of catalyst N3-750 2 The trend of the change of the Faraday efficiency of the reduction product can be seen from the graph, the current density of the reduction product is slightly reduced after 8 hours of electrolysis, and the Faraday efficiency of CO is reduced from 75.9% to 67.37%; CH (CH) 4 The faraday efficiency of (c) decreases from 0.78% to 0.65%. The results show that the catalyst has excellent stability.
Example 3
The Zn-N co-doped carbon aerogel catalyst is prepared by the embodiment, and the specific operation steps are as follows:
1g of potassium hydroxide, 6g of sodium hydroxide and 12g of urea are dissolved in 81g of deionized water and stirred uniformly, and the mixture is put into a refrigerator for freezing, and the precooling time is 2 hours, and the temperature is minus 12 ℃; taking out the pre-cooled solution, thawing to a non-ice state at room temperature, adding 5g of microcrystalline cellulose, and magnetically stirring for 2.5h; adding 9mL epichlorohydrin and 1.4g melamine, magnetically stirring for 2.5h, taking out the magnetons, and standing at room temperature for 4h to form hydrogel; washing with deionized water for 10 times to neutrality, and placing hydrogel into 1M ZnCl 2 Soaking the solution for 24 hours, wherein the step is to soak Zn 2+ Loaded onto the gel, and Cl - The presence of (2) will inhibit the occurrence of hydrogen evolution reactions; will contain Zn 2+ And the hydrogel of N is put into a freeze dryer for freeze drying, firstly put into a cold well for pre-cooling for 6 hours at the temperature of minus 55 ℃, then the sample is moved into a vacuum drying chamber, and the freeze drying time is 48 hours, thus obtaining Zn-N co-doped cellulose-based aerogel; placing the same four aerogels into a tube furnace, respectively heating to 650 ℃, 750 ℃, 850 ℃, 950 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to obtain four Zn-N co-doped carbon aerogels; grinding each obtained carbon aerogel into powder, dissolving in deionized water, ethanol and Nafion film solution for ultrasonic treatment for 0.5h, wherein the volume ratio of the deionized water to the ethanol to the Nafion film solution is 40:260:700 to obtain ink-like liquid, and coating the ink-like liquid on carbon paper with the volume of 1cm multiplied by 2cm to obtain the available electrocatalysts, namely Zn respectively 2+ +N-650、Zn 2+ +N-750、Zn 2+ +N-850 and Zn 2+ +N-950。
The electrolytic cell was assembled with reference to example 1, and the catalyst prepared in this example was tested for its ability to electrocatalytically reduce carbon dioxide. As can be seen from fig. 8, the catalyst (Zn 2+ The +N-T) limiting current density is far greater than that of pure carbon paper and can reach-28.67 mA cm at most -2 And the initial potential is at least-0.245V vs. RHE, which shows that the Zn-N co-doped carbon aerogel catalyst has stronger electrocatalytic activity. FIG. 9 is a catalyst Zn 2+ The Faraday efficiency of the +N-850 products at different potentials can be seen to be 89.45% for the CO product at-1.0V potential. FIG. 10 shows catalyst Zn 2+ Current density and CO after 8h of continuous electrolysis of +n-850 2 The trend of the change of the Faraday efficiency of the reduction product can be seen from the graph, the current density of the reduction product is slightly reduced after 8 hours of electrolysis, and the Faraday efficiency of CO is reduced from 89.45% to 88.1%; CH (CH) 4 The faraday efficiency of (c) decreases from 0.76% to 0.43%. The results show that the catalyst has excellent stability.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The preparation method of the metal/nonmetal co-doped carbon aerogel for electrocatalytic reduction of carbon dioxide is characterized by comprising the following steps of:
s1, dissolving cellulose or a derivative thereof in a urea alkali solution to obtain a precursor solution, wherein the urea alkali solution is urea aqueous solution containing sodium hydroxide and potassium hydroxide; the mass ratio of potassium hydroxide, sodium hydroxide, urea and water in the urea alkali solution is (1-2)/(3-8)/(10-15)/(80-100);
s2, adding a non-metal doping reagent and a cross-linking agent into the precursor solution, stirring, standing to obtain a non-metal doped hydrogel, and then soaking the non-metal doped hydrogel in a metal salt solution to obtain a metal/non-metal co-doped hydrogel;
the nonmetallic doping agent is one or more of boric acid, phosphoric acid, melamine, polyaniline and polypyrrole;
the metal salt solution is FeCl 3 、NiCl 2 、CoCl 2 、Cu(NO 3 ) 2 、CuCl 2 、ZnCl 2 And Zn (NO) 3 ) 2 One or more solutions of (a) and (b);
s3, freeze-drying the metal/nonmetal co-doped hydrogel to obtain metal/nonmetal co-doped aerogel;
and S4, carbonizing the metal/nonmetal co-doped aerogel at high temperature to obtain the metal/nonmetal co-doped carbon aerogel.
2. The method of manufacturing according to claim 1, characterized in that: in the step S1, the mass ratio of the cellulose or the derivative thereof, the potassium hydroxide, the sodium hydroxide, the urea and the water in the precursor solution is 5 (1-2)/(3-8)/(10-15)/(80-100).
3. The method of manufacturing according to claim 1, characterized in that: in the step S1, the urea alkali solution is precooled to the temperature of minus 20 ℃ to minus 10 ℃, and then the cellulose or the derivative thereof is immediately added and stirred, so that the cellulose or the derivative thereof is completely dissolved.
4. The method of manufacturing according to claim 1, characterized in that: in step S1, the cellulose or the derivative thereof is one or more of poly-polymerized cellulose, cellulose ether, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose and carboxymethyl cellulose.
5. The method of manufacturing according to claim 1, characterized in that: in the step S2, the time for soaking in the metal salt solution is 18-30 h.
6. The method of any one of claims 1-5, wherein: in the step S3, the pre-cooling temperature of freeze drying is minus 40 ℃ to minus 60 ℃ and the drying time is 36h to 72h.
7. The method according to any one of claims 1 to 5, wherein in step S4, the conditions of the high-temperature carbonization process are: and heating to 650-950 ℃ at a heating rate of 5-10 ℃ per minute, and preserving heat for 0.5-2 hours.
8. The application of the metal/nonmetal co-doped carbon aerogel in the electrocatalytic reduction of carbon dioxide is characterized in that: the catalyst used in the electrocatalytic reduction of carbon dioxide comprises a metal/nonmetal co-doped carbon aerogel prepared by the preparation method of any one of claims 1-7.
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| CN110801855A (en) * | 2018-08-06 | 2020-02-18 | 北京大学深圳研究生院 | Preparation method and application of transition metal and nitrogen co-doped carbon material |
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