CN114377717B - Lignin-based carbon composite graphite phase carbon nitride/Mxene heterojunction photocatalyst and preparation method and application thereof - Google Patents
Lignin-based carbon composite graphite phase carbon nitride/Mxene heterojunction photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 24
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title abstract description 15
- 229910002804 graphite Inorganic materials 0.000 title abstract description 5
- 239000010439 graphite Substances 0.000 title abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 56
- 230000001699 photocatalysis Effects 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000013032 photocatalytic reaction Methods 0.000 claims abstract description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 10
- 230000005496 eutectics Effects 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 5
- 238000004537 pulping Methods 0.000 claims abstract description 3
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 23
- 238000009210 therapy by ultrasound Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000370 acceptor Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 6
- 235000019743 Choline chloride Nutrition 0.000 claims description 6
- 229960003178 choline chloride Drugs 0.000 claims description 6
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 2
- 229960003237 betaine Drugs 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 4
- 239000000725 suspension Substances 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 229910052724 xenon Inorganic materials 0.000 claims 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 238000005286 illumination Methods 0.000 abstract description 5
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
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- 238000005530 etching Methods 0.000 abstract description 2
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- 238000013329 compounding Methods 0.000 abstract 1
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- 230000005494 condensation Effects 0.000 abstract 1
- 239000004020 conductor Substances 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 229920000877 Melamine resin Polymers 0.000 description 22
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 22
- 238000005070 sampling Methods 0.000 description 21
- 239000007788 liquid Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 8
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- -1 carbon aluminum titanium Chemical compound 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000004298 light response Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008176 lyophilized powder Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
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Classifications
-
- B01J35/39—
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
Abstract
The invention provides a heterojunction photocatalyst of lignin-based carbon composite graphite phase carbon nitride/Mxene, a preparation method and application thereof, wherein pulping alkali lignin is taken as a carbon source, and lignin-based nano carbon particles are sintered through eutectic solvent homogeneous phase dissolution; then urea is used as a raw material, graphite phase carbon nitride is prepared through a thermal condensation method and is used as a main body part of the photocatalyst; then taking titanium aluminum carbide as a raw material, and preparing a two-dimensional conductive material Mxene through hydrofluoric acid etching; finally, the lignin-based nano carbon is used for heat treatment and compounding of the g-C under the protection of inert gas 3 N 4 And Mxene, construction of C/g-C 3 N 4 The Mxene ternary heterojunction photocatalysis material. The heterojunction photocatalyst prepared by the method has the advantages of good illumination absorption, rapid photo-generated electron transfer, high photo-generated carrier separation efficiency and good photocatalytic reaction activity, and is an environment-friendly photocatalytic material which can prepare hydrogen peroxide under the photocatalysis of visible light.
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and in particular relates to lignin-based carbon composite g-C 3 N 4 Heterojunction photocatalyst of/Mxene, and preparation method and application thereof.
Background
Hydrogen peroxide (H) 2 O 2 ) Is a multifunctional oxidant with extremely wide application, and can be applied to the biological field, the environmental remediation field, the chemical field and the like. The hydrogen peroxide is generally weak in oxidizing property, the solution can be diluted for sterilization, and the final product after the reaction is mainly water, so that secondary pollution is avoided, and the hydrogen peroxide is an environment-friendly oxidant. The traditional method is not environment-friendly enough, so that the hydrogen peroxide is prepared by photocatalysis. In addition, the photocatalysis method does not need hydrogen, and is a safe and green method.
Graphite phase carbon nitride (g-C) 3 N 4 ) As an emerging nonmetallic two-dimensional material, the material has the advantages of easily available raw materials, simple and convenient synthesis, stable physical and chemical properties, no toxicity, adjustable visible light response and electronic properties and the like, and becomes one of hot materials in the field of photocatalysis in more than ten years. Despite the original g-C 3 N 4 Has a relatively ideal energy band structure, the theoretical forbidden bandwidth is about 2.7eV, belongs to visible light response, has stronger coulomb binding effect, and leads the g-C to be 3 N 4 Inevitably, carrier recombination is serious, and conductivity is poor. Although g-C 3 N 4 The two-dimensional lamellar is easy to agglomerate and stack in the actual preparation process, and the actual specific surface area often cannot reach a theoretical value, so that the lack of active sites is caused, and the photocatalytic performance is further compromised.
Mxene has proven to be a promising class of cocatalysts but has poor stability. In the research of this chapter, we succeeded in constructing a robust heterojunction photocatalyst in which few layers of Mxene are wrapped in g-C 3 N 4 In (3) the self-oxidation is prevented. The catalyst shows stable and efficient photocatalytic performance in hydrogen peroxide production.
Disclosure of Invention
The invention aims at the problems and provides a lignin-based carbon composite g-C 3 N 4 The heterojunction photocatalyst prepared by the preparation method of the heterojunction photocatalyst of/Mxene has better illumination absorption, rapid photogenerated electron transfer, higher photogenerated carrier separation efficiency and better photocatalytic reaction activity, and meanwhile, the heterojunction photocatalyst is an environment-friendly photocatalytic material and can be used for preparing hydrogen peroxide under the photocatalysis of visible light.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
(1) Alkali lignin treatment: and (3) placing 10-20 g of alkali lignin extracted from the pulping black liquor into a beaker, pouring 250-500 mL of dilute hydrochloric acid (0.1-0.5 mol/L), standing for 12-24 h, filtering, and finally placing into a blast drying oven for drying at 60-80 ℃ to obtain lignin.
(2) Preparation of lignin-based nanocarbon: firstly preparing a eutectic solvent, putting choline chloride serving as a hydrogen bond acceptor and thiourea (urea or betaine) serving as a hydrogen bond donor into a three-necked flask in a molar ratio of (1:1-1:5), reacting for 15-90 min in an oil bath pot (80-90 ℃), and after a clear and transparent solution is formed, preparing a solution with a mass ratio of 1: 3-1: 10 Adding lignin in the step (1) and continuously stirring, reacting for 12-24 hours, taking a proper amount of liquid, putting the liquid into a freezing bottle, freeze-drying for 12-24 hours, and grinding to obtain lignin freeze-dried powder.
（3）g-C 3 N 4 Is prepared from the following steps: taking melamine as a precursor, weighing 10-20 g of melamine, placing the melamine into a tube furnace at 450-550 ℃, and heating at 1-2 ℃/min to prepare g-C 3 N 4 。
(4) Mxene: weighing 0.5-1 g of commercially available carbon aluminum titanium Ti under continuous stirring (preventing solution from radiating and splashing) 3 AlC 2 Slowly adding the powder into a centrifuge tube filled with 40-80 mL of 40wt% hydrofluoric acid solution, and stirring for 24-48 h under the water bath heating condition of 25-50 ℃. And then, washing the precipitate by using deionized water for centrifugation (the rotating speed is 6000-9000 r/min) until the pH value of the supernatant is close to 7. Vacuum drying the obtained precipitate at 40-60 ℃ overnight to obtain an etching phaseTi of (2) 3 C 2 Black powder, noted Mxene.
（5）C/g-C 3 N 4 Preparation of a/Mxene ternary heterojunction photocatalytic material: placing 5-10mg of lignin freeze-dried powder into 5-20 mL of deionized water, performing ultrasonic treatment for 15-30 min, adding 5-10mg of Mxene, performing ultrasonic treatment for 15-30 min, and finally adding 1g g-C 3 N 4 Ultrasonic treatment is carried out for 15-30 min, the mixture is poured into a crucible after ultrasonic treatment is finished, a blast drying box is placed into the crucible for drying at 60-80 ℃ for 12-24 h, a sample is placed into a tubular furnace for 450-550 ℃ after the drying is finished, the temperature is 1-2 ℃/min, the temperature is kept for 0.5-1 h, and the lignin-based carbon composite g-C can be obtained under the protection of inert gas 3 N 4 Heterojunction photocatalyst of/Mxene.
C/g-C 3 N 4 Taking 50mg of the novel photocatalyst as a photocatalyst, placing the photocatalyst into 50mL of water solution, introducing oxygen, preparing hydrogen peroxide under the illumination condition of visible light, and testing the content of the hydrogen peroxide by using a POD/DPD method.
The invention has the following advantages:
1. lignin-based carbon composite g-C of the invention 3 N 4 The heterojunction photocatalyst of/Mxene takes industrial alkali lignin as a carbon precursor, so that the maximum utilization of resources is realized.
2. The invention adopts eutectic solvent to dissolve lignin, which is not only low in cost, but also green and environment-friendly, and has good dissolution effect.
3. The invention introduces Mxene and enhances the conductivity of carbon nitride.
4. The composite photocatalyst provided by the invention not only has excellent photocatalytic characteristics, but also has good visible light response performance; at the same time, C/g-C 3 N 4 The Mxene heterojunction photocatalytic material can endow continuous surface electron transmission advantages, and further improves the catalytic performance of the composite photocatalyst.
Drawings
FIG. 1 shows Mxene, g-C prepared in example 1 of the present invention 3 N 4 And Mxene/g-C 3 N 4 SEM images of (a);
FIG. 2 shows the g-C of example 1 of the present invention 3 N 4 And Mxene/g-C 3 N 4 Is a XRD pattern of (C).
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention.
Example 1
(1) Alkali lignin treatment: 20g of industrial alkali lignin is taken and put into a beaker, 500mL of diluted hydrochloric acid is poured into the beaker, the mixture is kept still for 24 hours, filtration is carried out, and finally the mixture is put into a blast drying oven for drying at 80 ℃.
(2) Preparation of lignin-based nanocarbon: firstly preparing a eutectic solvent, taking choline chloride as a hydrogen bond acceptor and thiourea as a hydrogen bond donor in a molar ratio of 1:2 is put into a three-neck flask, is reacted for 90min at 90 ℃ in an oil bath, and after clear and transparent solution is formed, the mass ratio is 1:3 (the sum of the mass of lignin, the mass of a hydrogen bond acceptor and the mass of a hydrogen bond donor) adding lignin, continuously stirring, taking a proper amount of liquid after reacting for 24 hours, putting the liquid into a freezing bottle, freeze-drying for 24 hours, and grinding to obtain lignin freeze-dried powder.
③g-C 3 N 4 Is prepared from the following steps: taking melamine as a precursor, weighing 10g of melamine, placing the melamine into a tubular furnace at 500 ℃, and heating at 2 ℃/min to prepare g-C 3 N 4 。
(4) Mxene: 1g of commercially available carbon aluminum titanium Ti was weighed with constant stirring (to prevent exothermic splashing of the solution) 3 AlC 2 The powder was slowly added to a centrifuge tube containing 80mL of 40% strength hydrofluoric acid solution and stirred for 48h under heating in a water bath at 50 ℃. The pellet was then washed by centrifugation with deionized water (rotational speed 9000 r/min) until the supernatant pH was near 7. Vacuum drying the precipitate at 60deg.C overnight to obtain etched phase Ti 3 C 2 Black powder, noted Mxene.
⑤C/g-C 3 N 4 Preparation of a/Mxene ternary heterojunction photocatalytic material: putting 5mg of freeze-dried powder into 10mL of deionized water, performing ultrasonic treatment for 30min, adding 5mg of Mxene, performing ultrasonic treatment for 30min, and finally adding 1gg-C 3 N 4 Ultrasonic for 30min, pouring into crucible after ultrasonic treatment, drying at 80deg.C in air drying oven for 24 hr, and collecting the productPlacing the sample into a tube furnace at 500 deg.C, 2 deg.C/min, maintaining the temperature for 1h, and under the protection of inert gas to obtain C/g-C 3 N 4 The Mxene ternary heterojunction photocatalysis material.
Photocatalytic reaction: 50mg C/g-C 3 N 4 Placing the Mxene ternary heterojunction photocatalytic material into a photocatalytic reaction device, adding 50mL water, reacting for 30min under the dark condition, sampling after dark absorption, starting a visible lamp to irradiate the solution after sampling, taking samples every 1h, immediately filtering all the sampled solution by using a filter membrane after sampling, placing the filtered solution into a 5 mL centrifuge tube for shading and sealing, finally testing the content of hydrogen peroxide by using a POD/DPD method, and measuring the absorbance of the hydrogen peroxide solution by using an ultraviolet-visible absorption light detector to obtain the hydrogen peroxide concentration of 1.2mmol/L.
FIG. 1 is a graph of Mxene and Mxene/g-C prepared in example 1 3 N 4 As can be seen from FIG. 1, mxene has a layered structure, and the carbon nitride precursor melamine has a g-C structure after one-step heat treatment 3 N 4 Overall in a block structure, g-C after loading Mxene and lignin based carbon 3 N 4 After heat treatment, a part of lignin is carbonized into small particles (shown by white circles) to be loaded on the surface of Mxene or enter gaps of the Mxene, and carbon nitride, mxene and lignin-based carbon are well combined. FIG. 2 is a graph of g-C prepared in example 1 3 N 4 And C/g-C 3 N 4 XRD patterns of Mxene As can be seen from FIG. 2, there appear two characteristic peaks typical of graphitic carbon nitrides, 12.9 o And 27.6 o Corresponding to (100) and (002) crystal planes, respectively; and C/g-C 3 N 4 33.9 of the/Mxene ternary heterojunction o 、38.9 o 、41.7 o 、60.1 o 、70.3 o 、73.9 o The new diffraction peaks are all characteristic peaks from Mxene, and in addition, due to the small amount of lignin-based diffraction carbon introduced into the ternary heterojunction, g-C 3 N 4 The (100) and (002) crystal face strength is weakened without affecting g-C 3 N 4 As a characteristic peak of the main catalyst.
Example 2
(1) Alkali lignin treatment: 20g of industrial alkali lignin is taken and put into a beaker, 500mL of diluted hydrochloric acid is poured into the beaker, the mixture is kept still for 24 hours, filtration is carried out, and finally the mixture is put into a blast drying oven for drying at 80 ℃.
(2) Preparation of lignin-based nanocarbon: firstly preparing a eutectic solvent, taking choline chloride as a hydrogen bond acceptor and thiourea as a hydrogen bond donor in a molar ratio of 1:2 is put into a three-neck flask, is reacted for 90min at 90 ℃ in an oil bath, and after clear and transparent solution is formed, the mass ratio is 1: and 5 (the sum of the mass of lignin, the mass of a hydrogen bond acceptor and the mass of a hydrogen bond donor) adding lignin, continuously stirring, taking a proper amount of liquid after reacting for 24 hours, putting the liquid into a freezing bottle, freeze-drying for 24 hours, and grinding to obtain lignin freeze-dried powder.
③g-C 3 N 4 Is prepared from the following steps: taking melamine as a precursor, weighing 10g of melamine, placing the melamine into a tubular furnace at 500 ℃, and heating at 2 ℃/min to prepare g-C 3 N 4 。
(4) Mxene: 1g of commercially available carbon aluminum titanium Ti was weighed with constant stirring (to prevent exothermic splashing of the solution) 3 AlC 2 The powder was slowly added to a centrifuge tube containing 80mL of 40% strength hydrofluoric acid solution and stirred for 48h under heating in a water bath at 50 ℃. The pellet was then washed by centrifugation with deionized water (rotational speed 9000 r/min) until the supernatant pH was near 7. Vacuum drying the precipitate at 60deg.C overnight to obtain etched phase Ti 3 C 2 Black powder, noted Mxene.
⑤C/g-C 3 N 4 Preparation of a/Mxene ternary heterojunction photocatalytic material: placing 10mg of lyophilized powder into 10mL of deionized water, performing ultrasonic treatment for 30min, adding 5mg of Mxene, performing ultrasonic treatment for 30min, and finally adding 1g g-C 3 N 4 Ultrasonic treatment for 30min, pouring into crucible after ultrasonic treatment, drying at 80deg.C for 24 hr in a blast drying oven, placing sample into tubular furnace at 500deg.C/min, maintaining at 2deg.C/min for 1 hr, and under the protection of inert gas to obtain C/g-C 3 N 4 The Mxene ternary heterojunction photocatalysis material.
Photocatalytic reaction: 50mg C/g-C 3 N 4 Placing the/Mxene ternary heterojunction photocatalytic material into a photocatalytic reaction device, adding 50mL water, reacting for 30min under the dark condition, sampling after dark adsorption, and starting a visible lamp for dissolving after samplingIrradiating the solution, sampling every 1h, filtering all the sampled solution by using a filter membrane immediately after sampling, putting the filtered solution into a 5 mL centrifuge tube for shading and sealing, finally testing the content of hydrogen peroxide by using a POD/DPD method, and measuring the absorbance of the hydrogen peroxide solution by using an ultraviolet-visible absorption light detector to obtain the hydrogen peroxide concentration of 0.75mmol/L.
Example 3
(1) Alkali lignin treatment: 20g of industrial alkali lignin is taken and put into a beaker, 500mL of diluted hydrochloric acid is poured into the beaker, the mixture is kept still for 24 hours, filtration is carried out, and finally the mixture is put into a blast drying oven for drying at 80 ℃.
(2) Preparation of lignin-based nanocarbon: firstly preparing a eutectic solvent, taking choline chloride as a hydrogen bond acceptor and urea as a hydrogen bond donor in a molar ratio of 1:3, placing the mixture into a three-neck flask, reacting for 60min at 90 ℃ in an oil bath, and after a clear and transparent solution is formed, mixing the materials according to a mass ratio of 1:3 (the sum of the mass of lignin, the mass of a hydrogen bond acceptor and the mass of a hydrogen bond donor) adding lignin, continuously stirring, taking a proper amount of liquid after reacting for 24 hours, putting the liquid into a freezing bottle, freeze-drying for 24 hours, and grinding to obtain lignin freeze-dried powder.
③g-C 3 N 4 Is prepared from the following steps: taking melamine as a precursor, weighing 10g of melamine, placing the melamine into a tubular furnace at 500 ℃, and heating at 2 ℃/min to prepare g-C 3 N 4 。
(4) Mxene: 1g of commercially available carbon aluminum titanium Ti was weighed with constant stirring (to prevent exothermic splashing of the solution) 3 AlC 2 The powder was slowly added to a centrifuge tube containing 80mL of 40% strength hydrofluoric acid solution and stirred for 48h under heating in a water bath at 50 ℃. The pellet was then washed by centrifugation with deionized water (rotational speed 9000 r/min) until the supernatant pH was near 7. Vacuum drying the precipitate at 60deg.C overnight to obtain etched phase Ti 3 C 2 Black powder, noted Mxene.
⑤C/g-C 3 N 4 Preparation of a/Mxene ternary heterojunction photocatalytic material: placing 10mg of lyophilized powder into 10mL of deionized water, performing ultrasonic treatment for 30min, adding 10mg of Mxene, performing ultrasonic treatment for 30min, and finally adding 1gg-C 3 N 4 Ultrasonic for 30min, pouring into crucible after ultrasonic treatment, drying at 80deg.C in air drying oven for 24 hr, and placing sample into tube after dryingHeat preservation is carried out for 1h at 500 ℃ and 2 ℃/min in a furnace, and C/g-C can be obtained under the protection of inert gas 3 N 4 The Mxene ternary heterojunction photocatalysis material.
Photocatalytic reaction: 50mg C/g-C 3 N 4 Placing the Mxene ternary heterojunction photocatalytic material into a photocatalytic reaction device, adding 50mL water, reacting for 30min under the dark condition, sampling after dark absorption, starting a visible lamp to irradiate the solution after sampling, taking samples every 1h, immediately filtering all the sampled solution by using a filter membrane after sampling, placing the filtered solution into a 5 mL centrifuge tube for shading and sealing, finally testing the content of hydrogen peroxide by using a POD/DPD method, and measuring the absorbance of the hydrogen peroxide solution by using an ultraviolet-visible absorption light detector to obtain the hydrogen peroxide concentration of 0.45mmol/L.
Comparative example 1
(1) Alkali lignin treatment: 20g of industrial alkali lignin is taken and put into a beaker, 500mL of diluted hydrochloric acid is poured into the beaker, the mixture is kept still for 24 hours, filtration is carried out, and finally the mixture is put into a blast drying oven for drying at 80 ℃.
(2) Preparation of lignin-based nanocarbon: firstly preparing a eutectic solvent, taking choline chloride as a hydrogen bond acceptor and thiourea as a hydrogen bond donor in a molar ratio of 1:2 is put into a three-neck flask, is reacted for 90min at 90 ℃ in an oil bath, and after clear and transparent solution is formed, the mass ratio is 1:3 (the sum of the mass of lignin, the mass of hydrogen bond acceptors and the mass of hydrogen bond donors) adding lignin, stirring continuously, taking a proper amount of liquid after reacting for 24 hours, putting the liquid into a freezing bottle, freeze-drying for 24 hours, and grinding to obtain the nano carbon freeze-dried powder.
③g-C 3 N 4 Is prepared from the following steps: taking melamine as a precursor, weighing 10g of melamine, placing the melamine into a tubular furnace at 500 ℃, and heating at 2 ℃/min to prepare g-C 3 N 4 。
④C/g-C 3 N 4 Binary heterojunction photocatalytic material preparation: putting 5mg of freeze-dried powder into 10mL of deionized water, performing ultrasonic treatment for 30min, and adding 1gg-C 3 N 4 Ultrasonic treatment for 30min, pouring into crucible after ultrasonic treatment, drying at 80deg.C for 24 hr in a blast drying oven, placing sample into tubular furnace at 500deg.C/min, maintaining at 2deg.C/min for 1 hr, and under the protection of inert gas to obtain C/g-C 3 N 4 Binary heterojunction photocatalysisA material.
Photocatalytic reaction: 50mg C/g-C 3 N 4 The binary heterojunction photocatalytic material is placed into a photocatalytic reaction device, 50mL water is added, reaction is carried out for 30min under the dark condition, sampling is carried out after dark absorption, a visible lamp is started to irradiate the solution after sampling, sampling is carried out once every 1h, all the sampled solution is immediately filtered by a filter membrane after sampling and placed into a 5 mL centrifuge tube for shading and sealing, finally the content of hydrogen peroxide is tested by using a POD/DPD method, and the absorbance of the hydrogen peroxide solution is measured by using an ultraviolet-visible absorption light detector, so that the hydrogen peroxide concentration is 0.2mmol/L.
Comparative example 2
①g-C 3 N 4 Is prepared from the following steps: taking melamine as a precursor, weighing 10g of melamine, placing the melamine into a tubular furnace at 500 ℃, and heating at 2 ℃/min to prepare g-C 3 N 4 。
(2) Mxene: 1g of commercially available carbon aluminum titanium Ti was weighed with constant stirring (to prevent exothermic splashing of the solution) 3 AlC 2 The powder was slowly added to a centrifuge tube containing 80mL of 40% strength hydrofluoric acid solution and stirred for 48h under heating in a water bath at 50 ℃. The pellet was then washed by centrifugation with deionized water (rotational speed 9000 r/min) until the supernatant pH was near 7. Vacuum drying the precipitate at 60deg.C overnight to obtain etched phase Ti 3 C 2 Black powder, noted Mxene.
③g-C 3 N 4 Preparation of a Mxene binary heterojunction photocatalytic material: putting 5mgMxene into 10mL deionized water, performing ultrasonic treatment for 30min, and adding 1gg-C 3 N 4 Ultrasonic for 30min, pouring into crucible after ultrasonic treatment, drying at 80deg.C for 24 hr in a blast drying oven, placing sample into tubular furnace at 500deg.C/min, maintaining at 2deg.C/min for 1 hr, and under inert gas protection to obtain g-C 3 N 4 Mxene binary heterojunction photocatalytic material.
Photocatalytic reaction: 50mg g-C 3 N 4 Placing the/Mxene binary heterojunction photocatalytic material into a photocatalytic reaction device, adding 50mL water, reacting for 30min under the dark condition, sampling after dark adsorption, starting a visible lamp to irradiate the solution after sampling, and taking samples every 1hAll the sampling solutions are filtered by a filter membrane and placed into a 5 mL centrifuge tube for shading and sealing immediately after sampling, finally, the content of hydrogen peroxide is tested by a POD/DPD method, and the absorbance of the hydrogen peroxide solution is measured by an ultraviolet-visible absorption light detector, so that the hydrogen peroxide concentration is 0.3mmol/L.
Comparative example 3
g-C 3 N 4 Is prepared from the following steps: taking melamine as a precursor, weighing 10g of melamine, placing the melamine into a tubular furnace at 500 ℃, and heating at 2 ℃/min to prepare g-C 3 N 4 。
Photocatalytic reaction: 50mg g-C 3 N 4 Placing the photocatalytic material into a photocatalytic reaction device, adding 50mL water, reacting for 30min under the dark condition, sampling after dark absorption, starting a visible lamp to irradiate the solution after sampling, sampling once every 1h, immediately filtering all the sampled solution by using a filter membrane after sampling, placing the filtered solution into a 5 mL centrifuge tube for shading and sealing, finally testing the content of hydrogen peroxide by using a POD/DPD method, and measuring the absorbance of the hydrogen peroxide solution by using an ultraviolet-visible absorption light detector to obtain the hydrogen peroxide concentration of 0.1mmol/L.
In the invention, carbon nitride is a main catalyst and is responsible for exciting photo-generated electrons and holes after illumination, and Mxene and lignin-based carbon are cocatalysts, so that the rapid transfer of electrons generated by carbon nitride is promoted, the separation and transfer of photo-generated carriers are improved, and the effect of photosynthesis of hydrogen peroxide is improved. After lignin-based carbon is added into the system, the electron transfer effect of Mxene can be further improved, and the Mxene needs to be stripped out of gaps, so that the filling of lignin-based nano carbon is facilitated. In the invention, photo-generated electrons excited by the carbon nitride conduction band can be combined with oxygen molecules to form superoxide radicals; and the valence band oxidizes water molecules to form protons which combine with superoxide radicals to form hydrogen peroxide. And the specific surface area and the electron transfer effect of the carbon nitride system can be improved by introducing a part of Mxene into the carbon nitride system.
The heterojunction photocatalyst prepared by the method has the advantages of good illumination absorption, rapid photo-generated electron transfer, high photo-generated carrier separation efficiency and good photocatalytic reaction activity, and is an environment-friendly photocatalytic material which can be used for preparing hydrogen peroxide under the photocatalysis of visible light.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that the specific embodiments described are illustrative only and not intended to limit the scope of the invention, and that equivalent modifications and variations of the invention in light of the spirit of the invention will be covered by the claims of the present invention.
Claims (7)
1. Lignin-based carbon composite g-C 3 N 4 The preparation method of the heterojunction photocatalyst of/Mxene is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Alkali lignin treatment: taking alkali lignin and dilute sulfuric acid extracted from pulping black liquor, magnetically stirring and mixing for 12-24 hours at room temperature, filtering and drying to obtain lignin;
(2) Preparation of lignin-based nanocarbon: preparing a eutectic solvent, taking choline chloride as a hydrogen bond acceptor, thiourea or urea or betaine as a hydrogen bond donor, reacting for 15-90 min at 80-90 ℃, adding lignin treated in the step (1) and continuously stirring after a clear and transparent solution is formed, performing freeze-drying for 12-24 h after reacting for 12-24 h, and grinding to obtain lignin freeze-dried powder;
（3）g-C 3 N 4 is prepared from the following steps: urea is used as a precursor, the temperature is increased to 450-550 ℃ in a tube furnace at a heating rate of 1-2 ℃/min, and the temperature is kept for 0.5-1 h, so as to obtain the g-C 3 N 4 ；
(4) Preparation of Mxene: slowly adding aluminum titanium carbide powder into hydrofluoric acid solution, stirring for 24-72 h under the water bath heating condition of 25-50 ℃, centrifuging with deionized water, washing the precipitate until the pH value of the supernatant is 7, and drying the obtained precipitate to obtain etched phase Ti 3 C 2 Black powder, noted Mxene;
（5）C/g-C 3 N 4 preparation of Mxene ternary heterojunction photocatalytic material: putting the lignin freeze-dried powder prepared in the step (2) into deionized water for ultrasonic dispersion uniformly, adding the Mxene prepared in the step (4),continuing to uniformly disperse by ultrasonic, and then adding the g-C prepared in the step (3) 3 N 4 Then uniformly dispersing by ultrasonic, drying at 60-80 ℃ for 12-24 hours after ultrasonic treatment, and performing heat treatment after drying to obtain lignin-based carbon composite g-C 3 N 4 Heterojunction photocatalyst of/Mxene;
the quality of lignin freeze-dried powder in the step (5) is 5-10mg, the quality of Mxene is 5-10mg, and g-C 3 N 4 Is 1g in mass;
the heat treatment in the step (5) is specifically as follows: under the protection of inert gas, the temperature is raised to 450-550 ℃ in a tube furnace at a heating rate of 1-2 ℃/min, and the temperature is kept for 0.5-1 h.
2. The method of manufacturing according to claim 1, characterized in that: in the step (1), the concentration of the dilute sulfuric acid is 0.1-0.5 mol/L.
3. The method of manufacturing according to claim 1, characterized in that: the molar ratio of hydrogen bond acceptor to hydrogen bond donor in step (2) is 1: 1-1: 5.
4. the method of manufacturing according to claim 1, characterized in that: the ratio of the mass of lignin to the sum of the mass of hydrogen bond acceptors and the mass of hydrogen bond donors in the step (2) is 1:3-1: 10.
5. a lignin-based carbon composite g-C prepared by the method of any one of claims 1-4 3 N 4 Heterojunction photocatalyst of/Mxene.
6. A lignin-based carbon composite g-C as recited in claim 5 3 N 4 Use of a heterojunction photocatalyst of/Mxene in the photocatalytic synthesis of hydrogen peroxide.
7. The use according to claim 6, characterized in that: photocatalytic reaction: taking lignin-based carbon composite g-C 3 N 4 Mixing the heterojunction photocatalyst of/Mxene with deionized water, reacting in the dark firstAfter adsorption balance, a visible light xenon lamp is started to irradiate the suspension.
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