CN117399022B - Lignin-based composite catalytic material and preparation method and application thereof - Google Patents
Lignin-based composite catalytic material and preparation method and application thereof Download PDFInfo
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- CN117399022B CN117399022B CN202311724801.8A CN202311724801A CN117399022B CN 117399022 B CN117399022 B CN 117399022B CN 202311724801 A CN202311724801 A CN 202311724801A CN 117399022 B CN117399022 B CN 117399022B
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- 229920005610 lignin Polymers 0.000 title claims abstract description 107
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 68
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 30
- 239000012266 salt solution Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 15
- 235000019253 formic acid Nutrition 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 150000001621 bismuth Chemical class 0.000 claims description 12
- 150000003681 vanadium Chemical class 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 3
- 150000002505 iron Chemical class 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 229910052797 bismuth Inorganic materials 0.000 abstract description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 15
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000003763 carbonization Methods 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 abstract description 4
- 239000002923 metal particle Substances 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 8
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 7
- 229960002089 ferrous chloride Drugs 0.000 description 7
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 7
- ZUVVLBGWTRIOFH-UHFFFAOYSA-N methyl 4-methyl-2-[(4-methylphenyl)sulfonylamino]pentanoate Chemical compound COC(=O)C(CC(C)C)NS(=O)(=O)C1=CC=C(C)C=C1 ZUVVLBGWTRIOFH-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical group [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000006249 magnetic particle Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalytic composite materials, and particularly discloses a lignin-based composite catalytic material, and a preparation method and application thereof. The invention uses coprecipitation reaction and carbonization reaction to prepare magnetic lignin carbon powder, and carries bismuth vanadate thereon by high-temperature calcination, and uses the high specific surface area and excellent adsorption property of the magnetic lignin carbon to effectively inhibit agglomeration of metal particles, thereby improving the catalytic activity of the catalytic material, and promotes the transformation of bismuth vanadate to monoclinic scheelite phase crystal form with better catalytic performance and smaller band gap energy after staged high-temperature calcination, thereby further improving the activity of the obtained lignin-based composite catalytic material. The invention effectively solves the problems of easy agglomeration, poor catalytic efficiency, low catalytic activity and complex preparation of the material for photocatalytic conversion of carbon dioxide in the prior art.
Description
Technical Field
The invention relates to the field of catalytic composite materials, and particularly discloses a lignin-based composite catalytic material, and a preparation method and application thereof.
Background
Since the greenhouse effect tends to be severe, it has been an extremely important issue in the environmental field to treat carbon dioxide. Carbon dioxide can be used as a carbon resource to synthesize important chemicals, and can also be used for supercritical substances, food additives and the like. Such as synthetic inorganic metal carbonate materials, methanol, methane, dimethyl ether, carboxylic acids, esters, and the like. Among them, the catalytic conversion of carbon dioxide into energy and chemical products is a powerful measure to solve the problems of fossil fuel combustion and energy shortage.
Photocatalytic conversion of carbon dioxide is one of the important ways to achieve efficient utilization of carbon dioxide. In the prior art, carbon dioxide photocatalytic reduction is reported to be carried out under ultraviolet light by using a composite oxide as a catalyst to prepare formic acid and methanol, but the catalyst material is easy to agglomerate, so that the number of effective active sites is reduced, and the catalytic efficiency is reduced. In recent years, bismuth vanadate semiconductor materials are applied to the field of photocatalytic conversion due to the fact that the bismuth vanadate semiconductor materials are nontoxic, low in cost, high in stability, easy to prepare, strong in visible ultraviolet light absorption and the like, but in practical degradation experiments, the bismuth vanadate semiconductor materials are limited in catalytic activity due to the fact that the bismuth vanadate semiconductor materials are small in specific surface area, narrow in energy band structure, easy to complex electron-hole, difficult to separate, and weak in surface adsorption capacity. Although the catalytic performance of bismuth vanadate can be improved by modifying the bismuth vanadate or compounding other materials at present, a better catalytic effect can not be achieved, and the obtained photocatalytic material is mostly used for degrading organic dye wastewater and is rarely reported in the related materials for catalytic conversion of carbon dioxide. Therefore, the research and development of the catalytic material for catalytic conversion of carbon dioxide, which has high catalytic activity, simple preparation and good stability, has important significance for relieving environmental pressure and energy crisis.
Disclosure of Invention
Aiming at the problems of easy agglomeration, poor catalytic efficiency, low catalytic activity and complex preparation of materials for photocatalytic conversion of carbon dioxide in the prior art, the invention provides a lignin-based composite catalytic material and a preparation method and application thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the first aspect of the invention provides a preparation method of a lignin-based composite catalytic material, which comprises the following steps:
step one, adding lignin into Fe 2+ And Fe (Fe) 3+ Uniformly mixing, adjusting the pH value to 10-11, reacting at 60-80 ℃, centrifuging, and drying to obtain lignin mixture;
calcining the lignin mixture at 500-600 ℃ in an inert atmosphere to obtain magnetic lignin carbon powder;
step three, dissolving soluble bismuth salt in an acid solution to obtain a bismuth salt solution; dissolving soluble vanadium salt in an alkali solution to obtain a vanadium salt solution; mixing the bismuth salt solution and the vanadium salt solution, and regulating the pH value to 8-8.5 to obtain a precursor solution;
uniformly mixing the magnetic lignin carbon powder and the precursor solution, performing hydrothermal reaction at 400-450 ℃ for 12-24 hours, filtering, washing and drying to obtain a primary sintered product;
and fifthly, calcining the primary sinter at 500-600 ℃ for 2.5-3.5 h in an inert atmosphere, and cooling to obtain the lignin-based composite catalytic material.
Compared with the prior art, the invention provides a preparation method of a lignin-based composite catalytic material, which utilizes lignin and Fe 2+ And Fe (Fe) 3+ Takes the magnetic lignin as a raw material and prepares the magnetic lignin through coprecipitation reaction and carbonization reactionCarbon powder. Wherein, lignin is a space reticular structure, the molecular skeleton of the lignin contains rich functional groups and Fe generated by a coprecipitation method 3 O 4 The magnetic lignin carbon has strong adsorption performance, and after high-temperature carbonization, the lattice structure of the magnetic particles and the lignin framework are reformed at high temperature, the magnetic particles enter the lignin framework, the lignin is endowed with magnetism, and the obtained magnetic lignin carbon has excellent adsorption performance and high specific surface area.
The adsorption and catalytic performance of the magnetic lignin carbon are further improved by introducing bismuth vanadate. The magnetic lignin carbon is used as a carrier of a catalytic material, has high specific surface area and excellent adsorption performance, and is beneficial to Bi 3+ The method is beneficial to inhibiting agglomeration of metal particles, so that the catalytic activity of the material is improved, the segmented calcination can further promote the transformation of bismuth vanadate to a monoclinic scheelite phase crystal form with minimum band gap energy, change the crystallinity of the bismuth vanadate, reduce the recombination of photo-generated electrons and holes, enhance the capability of the catalytic material for capturing protons or electrons, improve the activity of the photocatalyst, and reduce the band gap energy of the bismuth vanadate, so that the obtained catalytic material can respond to visible light.
Preferably, in the first step, the lignin is any one or more of alkali lignin, sodium lignin sulfonate, calcium lignin sulfonate and sulfonated alkali lignin.
Most of lignin is industrial lignin, the cost is low, the molecule is of a space network structure, the molecular skeleton of the lignin contains more functional groups, and the lignin is easy to form firm combination with the surface of the magnetic particles.
Preferably, in the first step, the mass ratio of the lignin to the ferric salt solution is 1-3:100-300.
Preferably, in step one, fe in the ferric salt solution 2+ With Fe 3+ The molar ratio of (2) is 1:1-1.1.
Preferably, in step one, fe in the ferric salt solution 3+ The concentration of (C) is 0.01mol/L to 0.02mol/L.
Preferably, in the first step, the reaction time is 20min-30min.
Preferably, in the first step, the rotational speed of the centrifugation is 1500r/min-2500r/min.
Preferably, in the first step, the centrifugation time is 5min-10min.
Preferably, in the first step, the drying temperature is 90-120 ℃ and the drying time is 2-3 h.
Preferably, in the second step, the calcination time is 1.5h-2h.
Preferably, in the third step, the soluble bismuth salt is bismuth nitrate.
Preferably, in the third step, the soluble vanadium salt is any one of sodium metavanadate or ammonium metavanadate.
Preferably, in the third step, bi in the bismuth salt solution 3+ The concentration of (C) is 0.01mol/L to 0.05mol/L.
Preferably, in the third step, VO in the vanadium salt solution 3 - The concentration of (C) is 0.05mol/L to 0.2mol/L.
Preferably, in the third step, the acid solution is a nitric acid solution with the concentration of 0.05mol/L to 0.1 mol/L.
Preferably, in the third step, the alkali solution is sodium hydroxide solution with the concentration of 0.05mol/L to 0.1 mol/L.
Preferably, in the third step, the mass ratio of the bismuth salt solution to the vanadium salt solution is 1:0.9-1.2.
Preferably, in the fourth step, the mass ratio of the magnetic lignin carbon powder to the precursor solution is 1-1.5:1.
Preferably, in the fifth step, the temperature is raised to 500-600 ℃ by adopting a temperature programming mode, and the temperature raising rate of the temperature programming is 5-10 ℃/min.
The second aspect of the invention provides a lignin-based composite catalytic material, which is prepared by using the preparation method of the lignin-based composite catalytic material.
The third aspect of the invention provides an application of the lignin-based composite catalytic material in catalyzing carbon dioxide to prepare formic acid.
Preferably, the application of the lignin-based composite catalytic material in catalyzing carbon dioxide to prepare formic acid is performed under visible light.
Further preferably, the light source of visible light is a xenon lamp.
Further preferably, the wavelength of the xenon lamp is more than or equal to 420nm.
In summary, the invention provides the lignin-based composite catalytic material, the magnetic lignin carbon powder is prepared through coprecipitation reaction and carbonization reaction, and bismuth vanadate is loaded on the magnetic lignin carbon powder through high-temperature calcination, so that the agglomeration of metal particles is effectively inhibited by utilizing the high specific surface area and excellent adsorption performance of the magnetic lignin carbon, and the catalytic activity of the catalytic material is improved. And the bismuth vanadate is subjected to sectional high-temperature calcination to promote the transformation of the monoclinic scheelite phase crystal form with better catalytic performance and smaller band gap energy, so that the crystallinity of the monoclinic scheelite phase crystal form is changed, the electron-hole recombination is effectively avoided, the activity of the obtained lignin-based composite catalytic material is further improved, and the band gap energy of the bismuth vanadate is reduced to promote the obtained lignin-based composite catalytic material to catalyze the visible light response. The lignin-based composite catalytic material prepared by the method is used for catalyzing carbon dioxide to prepare formic acid, the yield of the obtained formic acid can reach 45.84mmol, and the TOF value of the lignin-based composite catalytic material can reach 13.19h -1 。
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a lignin-based composite catalytic material, which specifically comprises the following steps:
step one, dispersing 2g lignin in 100mL Fe 2+ And Fe (Fe) 3+ Wherein the mixed ferric salt solution contains 0.27g of ferric chloride hexahydrate and 0.20g of ferrous chloride tetrahydrate, the two are uniformly mixed, and sodium hydroxide with the concentration of 0.05mol/L is addedRegulating the pH of the solution to 10.3, reacting at 75 ℃ for 30min, centrifuging the system at 2000r/min for 5min after the reaction is finished, discarding the supernatant, and drying the obtained solid matter at 100 ℃ for 2.5h to obtain a lignin mixture;
calcining the lignin mixture at 550 ℃ for 1.5 hours in an inert atmosphere to obtain magnetic lignin carbon powder;
step three, 9.7g of bismuth nitrate pentahydrate is dissolved in 10mL of 0.05mol/L nitric acid solution to obtain solution A, 12.1g of sodium metavanadate is dissolved in 10mL of 0.05mol/L sodium hydroxide solution to obtain solution B, and the solution A and the solution B are mixed according to the mass ratio of 1:1, and the pH value is adjusted to 8.2 to obtain precursor solution;
uniformly mixing the magnetic lignin carbon powder and the precursor solution according to the mass ratio of 1:1, transferring into a reaction kettle, heating to 420 ℃, preserving heat for 15 hours, filtering, and washing with deionized water for 5 times to obtain a primary sinter;
and fifthly, under an inert atmosphere, secondarily heating the primary sinter to 550 ℃ at a heating rate of 8 ℃/min, calcining for 3 hours, and cooling to obtain the lignin-based composite catalytic material.
Example 2
The embodiment provides a lignin-based composite catalytic material, which specifically comprises the following steps:
step one, dispersing 2g lignin in 100mL Fe 2+ And Fe (Fe) 3+ Wherein the mixed ferric salt solution contains 0.27g of ferric chloride hexahydrate and 0.20g of ferrous chloride tetrahydrate, the ferric chloride hexahydrate and the ferrous chloride tetrahydrate are uniformly mixed, a sodium hydroxide solution with the concentration of 0.05mol/L is added to adjust the pH value to 10.8, the mixture reacts for 25min at the temperature of 70 ℃, after the reaction is finished, the system is centrifuged for 5min at the rotating speed of 2000r/min, the supernatant is discarded, and the obtained solid substance is dried for 2.5h at the temperature of 100 ℃ to obtain a lignin mixture;
calcining the lignin mixture at 580 ℃ for 1.5h in an inert atmosphere to obtain magnetic lignin carbon powder;
step three, 9.7g of bismuth nitrate pentahydrate is dissolved in 10mL of 0.05mol/L nitric acid solution to obtain solution A, 17.55g of ammonium metavanadate is dissolved in 10mL of 0.08mol/L sodium hydroxide solution to obtain solution B, and the solution A and the solution B are mixed according to the mass ratio of 1:1, and the pH value is adjusted to 8.3 to obtain precursor solution;
uniformly mixing the magnetic lignin carbon powder and the precursor solution according to the mass ratio of 1.1:1, transferring into a reaction kettle, heating to 430 ℃, preserving heat for 14 hours, filtering, and washing for 4 times by adopting deionized water to obtain a primary sinter;
and fifthly, in an inert atmosphere, secondarily heating the primary sinter to 520 ℃ at a heating rate of 6 ℃/min, calcining for 3.5h, and cooling to obtain the lignin-based composite catalytic material.
Example 3
The embodiment provides a lignin-based composite catalytic material, which specifically comprises the following steps:
step one, dispersing 2g lignin in 100mL Fe 2+ And Fe (Fe) 3+ Wherein the mixed ferric salt solution contains 0.27g of ferric chloride hexahydrate and 0.20g of ferrous chloride tetrahydrate, the ferric chloride hexahydrate and the ferrous chloride tetrahydrate are uniformly mixed, a sodium hydroxide solution with the concentration of 0.05mol/L is added to adjust the pH value to 10.8, the mixture reacts for 25min at 80 ℃, after the reaction is finished, the system is centrifuged for 5min at the rotating speed of 2000r/min, the supernatant is discarded, and the obtained solid substance is dried for 2.5h at 100 ℃ to obtain a lignin mixture;
calcining the lignin mixture for 2 hours at 520 ℃ in an inert atmosphere to obtain magnetic lignin carbon powder;
step three, dissolving 15.24g of bismuth nitrate pentahydrate in 10mL of 0.05mol/L nitric acid solution to obtain solution A, dissolving 22.13g of ammonium metavanadate in 10mL of 0.08mol/L sodium hydroxide solution to obtain solution B, mixing the solution A and the solution B according to a mass ratio of 1:1.1, and adjusting the pH value to 8.5 to obtain precursor solution;
uniformly mixing the magnetic lignin carbon powder and the precursor solution according to the mass ratio of 1.2:1, transferring into a reaction kettle, heating to 430 ℃, preserving heat for 16 hours, filtering, and washing with deionized water for 5 times to obtain a primary sinter;
and fifthly, under an inert atmosphere, secondarily heating the primary sinter to 550 ℃ at a heating rate of 10 ℃/min, calcining for 3 hours, and cooling to obtain the lignin-based composite catalytic material.
Comparative example 1
This comparative example provides a lignin-based composite catalytic material, which differs from example 1 in that: the magnetic lignin carbon is replaced by equivalent lignin carbon, other components and steps are unchanged, and the method specifically comprises the following steps:
calcining the lignin mixture at 550 ℃ for 1.5 hours in an inert atmosphere to obtain lignin carbon powder;
step two, 9.7g of bismuth nitrate pentahydrate is dissolved in 10mL of 0.05mol/L nitric acid solution to obtain solution A, 12.1g of sodium metavanadate is dissolved in 10mL of 0.05mol/L sodium hydroxide solution to obtain solution B, and the solution A and the solution B are mixed according to the mass ratio of 1:1, and the pH value is adjusted to 8.2 to obtain precursor solution;
step three, uniformly mixing the lignin carbon powder and the precursor solution according to the mass ratio of 1:1, transferring into a reaction kettle, heating to 420 ℃, preserving heat for 15 hours, filtering, and washing with deionized water for 5 times to obtain a primary sintered product;
and step four, under the inert atmosphere, the primary sinter is heated to 550 ℃ for a second time at a heating rate of 8 ℃/min, calcined for 3 hours, and cooled to obtain the lignin-based composite catalytic material.
Comparative example 2
This comparative example provides a composite catalytic material, which differs from example 1 in that: the magnetic lignin carbon is replaced by equivalent titanium dioxide, other components and steps are unchanged, and the method specifically comprises the following steps:
step one, 9.7g of bismuth nitrate pentahydrate is dissolved in 10mL of 0.05mol/L nitric acid solution to obtain solution A, 12.1g of sodium metavanadate is dissolved in 10mL of 0.05mol/L sodium hydroxide solution to obtain solution B, and the solution A and the solution B are mixed according to the mass ratio of 1:1, and the pH value is adjusted to 8.2 to obtain precursor solution;
uniformly mixing the titanium dioxide and the precursor solution according to the mass ratio of 1:1, transferring into a reaction kettle, heating to 420 ℃, preserving heat for 15 hours, filtering, and washing with deionized water for 5 times to obtain a primary sintered product;
and thirdly, under the inert atmosphere, secondarily heating the primary sinter to 550 ℃ at the heating rate of 8 ℃/min, calcining for 3 hours, and cooling to obtain the composite catalytic material.
Comparative example 3
This comparative example provides a lignin-based composite catalytic material, which differs from example 1 in that: the precursor solution is replaced by an equivalent ferric chloride solution, and the method specifically comprises the following steps of:
step one, dispersing 2g lignin in 100mL Fe 2+ And Fe (Fe) 3+ Wherein the mixed ferric salt solution contains 0.27g of ferric chloride hexahydrate and 0.20g of ferrous chloride tetrahydrate, the ferric chloride hexahydrate and the ferrous chloride tetrahydrate are uniformly mixed, a sodium hydroxide solution with the concentration of 0.05mol/L is added to adjust the pH value to 10.3, the mixture reacts for 30min at the temperature of 75 ℃, after the reaction is finished, the system is centrifuged for 5min at the rotating speed of 2000r/min, the supernatant is discarded, and the obtained solid substance is dried for 2.5h at the temperature of 100 ℃ to obtain a lignin mixture;
calcining the lignin mixture at 550 ℃ for 1.5 hours in an inert atmosphere to obtain magnetic lignin carbon powder;
step three, uniformly mixing the magnetic lignin carbon powder and the ferric chloride solution according to the mass ratio of 1:1, transferring into a reaction kettle, heating to 420 ℃, preserving heat for 15 hours, filtering, and washing with deionized water for 5 times to obtain a primary sinter;
and step four, under the inert atmosphere, the primary sinter is heated to 550 ℃ for a second time at a heating rate of 8 ℃/min, calcined for 3 hours, and cooled to obtain the lignin-based composite catalytic material.
In order to further embody the technical effects of the lignin-based composite catalytic material provided by the invention, the catalytic effect test is carried out on the lignin-based composite catalytic material obtained in the examples 1-3 and the comparative examples 1-3, and the specific test method is as follows:
(1) The lignin-based composite catalytic material and 100mL of 0.05mol/L NaHCO 3 The solution is put into a reactor with the volume of 5L, the reactor is provided with a gas inlet and a gas outlet, and the top is made of transparent quartzThe glass plate is sealed, a light source is arranged above the top of the reactor, the light source is a xenon lamp, the wavelength of the xenon lamp is 420nm, and the radiation illuminance is 302.6 mu W/cm 2 ；
(2) Opening a gas inlet and a gas outlet of the reactor, and introducing CO at a flow rate of 100mL/min 2 20min, and then H is introduced into the reaction system at a flow rate of 100mL/min 2 And (3) closing a gas inlet and a gas outlet for 20min, opening a xenon lamp, performing photocatalytic reaction, detecting the concentration of formic acid in a product by utilizing high performance liquid chromatography after the reaction is performed for 8 hours, and calculating the yield and catalytic TOF value of the obtained formic acid, wherein the calculation formula is as follows: tof=formic acid concentration/(catalyst concentration×reaction time), where formic acid concentration and catalyst concentration are in mg/L and reaction time is in h, and the results are shown in table 1.
Table 1 test results of lignin-based composite catalytic materials obtained in examples and comparative examples
As can be seen from Table 1, the lignin-based composite catalytic material provided by examples 1-3 of the present invention can catalyze the conversion of carbon dioxide into formic acid, and has high catalytic activity, and TOF value can reach 13.19h at most -1 The highest content of the obtained formic acid can reach 45.84mmol, which also proves that the lignin-based composite catalytic material provided by the invention has excellent catalytic performance.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (4)
1. The application of the lignin-based composite catalytic material in preparing formic acid by photocatalysis of carbon dioxide is characterized in that: the preparation method of the lignin-based composite catalytic material comprises the following steps:
step one, adding lignin into Fe 2+ And Fe (Fe) 3+ Uniformly mixing, regulating pH to 10-11, and adding into iron salt solution of 6Reacting at 0-80 ℃, centrifuging and drying to obtain lignin mixture;
calcining the lignin mixture at 500-600 ℃ in an inert atmosphere to obtain magnetic lignin carbon powder;
step three, dissolving soluble bismuth salt in an acid solution to obtain a bismuth salt solution; dissolving soluble vanadium salt in an alkali solution to obtain a vanadium salt solution; mixing the bismuth salt solution and the vanadium salt solution, and regulating the pH value to 8-8.5 to obtain a precursor solution;
uniformly mixing the magnetic lignin carbon powder and the precursor solution, performing hydrothermal reaction at 400-450 ℃ for 12-24 hours, filtering, washing and drying to obtain a primary sintered product;
calcining the primary sinter at 500-600 ℃ for 2.5-3.5 h under inert atmosphere, and cooling to obtain a lignin-based composite catalytic material;
in the first step, the lignin is any one or more of alkali lignin, sodium lignin sulfonate, calcium lignin sulfonate or sulfonated alkali lignin;
in the first step, the mass ratio of the lignin to the ferric salt solution is 1-3:100-300;
in the first step, fe in the ferric salt solution 2+ With Fe 3+ The molar ratio of (2) is 1:1-1.1;
in the first step, fe in the ferric salt solution 3+ The concentration of (2) is 0.01mol/L-0.02mol/L;
in the second step, the calcination time is 1.5h-2h;
in the third step, bi in the bismuth salt solution 3+ The concentration of (2) is 0.01mol/L-0.05mol/L;
in the third step, VO in the vanadium salt solution 3 - The concentration of (2) is 0.05mol/L-0.2mol/L;
in the third step, the acid solution is nitric acid solution with the concentration of 0.05mol/L-0.1 mol/L;
in the third step, the alkali solution is sodium hydroxide solution with the concentration of 0.05mol/L-0.1 mol/L;
in the third step, the mass ratio of the bismuth salt solution to the vanadium salt solution is 1:0.9-1.2;
in the fourth step, the mass ratio of the magnetic lignin carbon powder to the precursor solution is 1-1.5:1.
2. The use of the lignin-based composite catalytic material according to claim 1 for the photocatalytic production of formic acid from carbon dioxide, wherein: in the first step, the reaction time is 20min-30min.
3. The use of the lignin-based composite catalytic material according to claim 1 for the photocatalytic production of formic acid from carbon dioxide, wherein: in the third step, the soluble bismuth salt is bismuth nitrate; and/or
In the third step, the soluble vanadium salt is any one of sodium metavanadate or ammonium metavanadate.
4. The use of the lignin-based composite catalytic material according to claim 1 for the photocatalytic production of formic acid from carbon dioxide, wherein: and fifthly, heating to 500-600 ℃ by adopting a temperature programming mode, wherein the temperature programming heating rate is 5-10 ℃/min.
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