CN112007684B - g-C3N4/C/Fe2O3Composite photocatalyst and preparation method thereof - Google Patents
g-C3N4/C/Fe2O3Composite photocatalyst and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 102000008186 Collagen Human genes 0.000 claims abstract description 26
- 108010035532 Collagen Proteins 0.000 claims abstract description 26
- 229920001436 collagen Polymers 0.000 claims abstract description 26
- 239000000835 fiber Substances 0.000 claims abstract description 26
- 239000010985 leather Substances 0.000 claims abstract description 26
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 19
- 239000004640 Melamine resin Substances 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 150000002505 iron Chemical class 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000011259 mixed solution Substances 0.000 claims description 39
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- 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 11
- 235000019253 formic acid Nutrition 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000004280 Sodium formate Substances 0.000 claims description 6
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 6
- 235000019254 sodium formate Nutrition 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 229910002804 graphite Inorganic materials 0.000 abstract description 15
- 239000010439 graphite Substances 0.000 abstract description 15
- 238000005215 recombination Methods 0.000 abstract description 7
- 230000006798 recombination Effects 0.000 abstract description 7
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003610 charcoal Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 239000011651 chromium Substances 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000002238 attenuated effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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Abstract
The invention belongs to the technical field of preparation of novel photocatalyst materials, and discloses g-C3N4/C/Fe2O3A composite photocatalyst and a preparation method thereof. The method comprises the following steps: tanning the leather collagen fibers with iron salt to obtain a first intermediate; retanning the first intermediate and melamine resin to obtain a second intermediate; and calcining the second intermediate under an inert gas atmosphere. The composite photocatalyst is prepared, wherein graphite phase carbon nitride is stably fixed on a porous charcoal material, and the g-C is prepared at the same time3N4/C/Fe2O3The composite photocatalyst material has large specific surface area and low recombination rate of photo-generated electron-hole pairs, and the catalysis efficiency of hexavalent chromium is remarkably improved.
Description
Technical Field
The invention relates to the technical field of preparation of novel photocatalyst materials, in particular to g-C3N4/C/Fe2O3A composite photocatalyst and a preparation method thereof.
Background
At present, methods for removing cr (vi) from industrial wastewater include adsorption, chemical precipitation, membrane separation, ion exchange, and photocatalytic techniques. Among them, the photocatalytic technology is considered as a promising technology due to its advantages such as low cost, high efficiency, environmental protection, etc.
Graphite phase carbon nitride (g-C)3N4) The polymer is a polymer with a layered structure, has low forbidden bandwidth, and is widely applied to photocatalysis due to the advantages of adjustable electronic structure, easy synthesis, physical and chemical stability and the like. In the prior art, the preparation method of carbon nitride generally comprises the step of directly calcining prepolymers such as melamine or ureaThe graphite-phase carbon nitride prepared by the method is small in specific surface area, blocky, low in light energy utilization rate and high in electron-hole pair recombination rate, and seriously hinders Cr (VI) from being in full contact with photo-generated electrons transferred to the surface of a photocatalyst, so that the photocatalytic activity of the photo-generated electrons is directly influenced, and the photocatalytic performance is poor.
Disclosure of Invention
In order to solve the problems in the background art, the invention aims to provide a composite material used as a photocatalyst, which has large specific surface area and low recombination rate of photo-generated electron-hole pairs and can efficiently treat hexavalent chromium.
In order to achieve the purpose, the invention adopts the technical scheme that:
g-C3N4/C/Fe2O3a preparation method of a composite photocatalyst, which comprises the following steps:
tanning the leather collagen fibers with iron salt to obtain a first intermediate;
retanning the first intermediate and melamine resin to obtain a second intermediate; and
the second intermediate is calcined under an inert gas atmosphere.
Furthermore, the leather collagen fiber can be prepared by crushing waste leather leftover materials from leather factories.
Further, the method for tanning hide collagen fibers with an iron salt comprises:
soaking the collagen fibers in water;
dissolving ferric salt in water, and adding the dissolved ferric salt into the soaked collagen fiber solution to obtain a first mixed solution;
the pH of the first mixed solution is adjusted.
Further, the method for adjusting the pH value of the first mixed solution comprises: the pH of the first solution was adjusted to 2.0 with a saturated sodium bicarbonate solution, and after 4h, the pH was adjusted to 4.0 with a saturated sodium bicarbonate solution.
Further, the mass ratio of the collagen fiber to the iron salt is 1: (0.75 to 1.5).
Further, the weight ratio of the first intermediate (on a dry basis) to the melamine resin is (5-10): 1.
further, the method for retanning the first intermediate with melamine resin comprises:
soaking the first intermediate with water;
adjusting the pH value of the mixed solution of the first intermediate and water;
adding melamine resin into the mixed solution with the adjusted pH value to react to obtain a second mixed solution;
adjusting the pH value of the second mixed solution; and
and washing and drying the collagen fibers in the second mixed solution after the pH value is adjusted.
Further, the method for adjusting the pH value of the mixed solution of the first intermediate and water comprises:
and adding a saturated sodium bicarbonate solution and a sodium formate solution with the mass percentage concentration of 2% into the mixed solution of the first intermediate and the water, stirring for 1.5h at the temperature of 35-40 ℃, and adjusting the pH value to 5.0-5.5.
Further, the method for adjusting the pH value of the second mixed solution comprises: and adding 2% by mass of formic acid into the second mixed solution, and adjusting the pH value to 3.5-3.8.
Further, the method for calcining the second intermediate under the inert gas atmosphere is divided into two stages, and the specific method comprises the following steps:
placing the second intermediate in an inert gas atmosphere, heating to 400 ℃, preserving heat for 2 hours and cooling to room temperature to obtain a biochar material;
mixing the biochar material with a KOH solution for reaction and then drying; and
and (3) putting the dried solid substance in an inert gas atmosphere, heating to 600 ℃, preserving the heat for 2h, cooling, washing and drying.
Further, the weight ratio of the biochar material to the KOH solution is 1: (2-4), wherein the mass concentration of the KOH solution is 4 mol/L.
The invention also discloses g-C prepared by any one of the methods3N4/C/Fe2O3A composite photocatalyst is provided.
Compared with the prior art, the invention has the following beneficial effects:
the invention combines the iron element with the carboxyl coordination on the collagen fiber to form a cross-linking bond, namely the iron element is loaded on the collagen fiber; retanning by reacting hydroxyl on hydroxylated melamine resin with amino on leather collagen fiber, and finally calcining step by step; the melamine resin and the groups on the collagen fiber are combined through chemical reaction, and can be stably fixed on the porous charcoal material by graphite-phase carbon nitride. Preparation of g-C simultaneously3N4/C/Fe2O3The composite photocatalyst material has large specific surface area and low recombination rate of photo-generated electron-hole pairs, and improves the catalysis efficiency of hexavalent chromium.
The composite photocatalyst is prepared by processing waste leather leftover materials of leather factories as raw materials, has low cost and can realize secondary utilization of wastes.
Drawings
FIG. 1 is an SEM image of pure graphite phase carbon nitride and a product of example 5 of the present invention and a mapping image of iron element of the product of example 5;
FIG. 2 is a BET plot of pure graphite phase carbon nitride and products of examples 5-7 of the present invention;
FIG. 3 is an XPS plot of pure graphite phase carbon nitride versus a product of example 5 of the present invention;
FIG. 4 is an XRD pattern of pure graphite phase carbon nitride and products of examples 5-7 of the present invention;
FIG. 5 is a DRS diagram and forbidden band width of pure graphite-phase carbon nitride and products of examples 5-7 of the present invention;
FIG. 6 is a PL diagram of pure graphite phase carbon nitride with products of examples 5-7 of the present invention;
FIG. 7 is a graph showing the effect of pure graphite phase carbon nitride on the photocatalytic reduction of hexavalent chromium in the products of examples 5 to 7 according to the present invention;
FIG. 8 is a graph of a cycle test of a product of example 5 of the present invention.
Detailed Description
In order to better understand the technical solution of the present invention, the technical solution of the present invention will be further described with reference to the accompanying drawings and examples. The mode for carrying out the present invention includes, but is not limited to, the following examples, which are provided to illustrate the present invention but not to limit the scope of the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The test methods in the following examples are conventional methods unless otherwise specified.
Example 1
g-C3N4/C/Fe2O3A preparation method of a composite photocatalyst, which comprises the following steps:
tanning the leather collagen fibers with iron salt to obtain a first intermediate;
retanning the first intermediate and melamine resin to obtain a second intermediate; and
the second intermediate is calcined under an inert gas atmosphere.
Wherein the mass ratio of the collagen fiber to the ferric salt is 1: (0.75 to 1.5); the weight ratio of the first intermediate (on a dry basis) to the melamine resin is (5-10): 1.
example 2
The method for tanning hide collagen fibers by using iron salt specifically comprises the following steps:
soaking the collagen fibers in water;
dissolving ferric salt in water, and adding the dissolved ferric salt into the soaked collagen fiber solution to obtain a first mixed solution;
adjusting the pH value of the first mixed solution; and
and washing and drying the collagen fibers in the first mixed solution.
Wherein the leather collagen fiber can be derived from waste leather leftover materials of leather factories and is prepared by crushing; the method for adjusting the pH value of the first mixed solution comprises the following steps: the pH of the first solution was adjusted to 2.0 with a saturated sodium bicarbonate solution, and after 4h, the pH was adjusted to 4.0 with a saturated sodium bicarbonate solution.
Example 3
The method of retanning a first intermediate with a melamine resin comprises:
soaking the first intermediate with water;
adjusting the pH value of the mixed solution of the first intermediate and water;
adding melamine resin into the mixed solution with the adjusted pH value to react to obtain a second mixed solution;
adjusting the pH value of the second mixed solution; and
and washing the collagen fibers in the second mixed solution after the pH value is adjusted.
The method for adjusting the pH value of the mixed solution of the first intermediate and the water comprises the following steps:
and adding a saturated sodium bicarbonate solution and a sodium formate solution with the mass percentage concentration of 2% into the mixed solution of the first intermediate and the water, stirring for 1.5h at the temperature of 35-40 ℃, and adjusting the pH value to 5.0-5.5.
The method for adjusting the pH value of the second mixed solution comprises the following steps: adding 2% by mass of formic acid into the second mixed solution, and adjusting the pH value to 3.5-3.8; wherein, the formic acid is added in two times, half of the formic acid is added in the first time, and the other half is added after the reaction is carried out for 30 min.
Example 4
The method for calcining the second intermediate under the inert gas atmosphere is divided into two stages, and the specific method comprises the following steps:
placing the second intermediate in an inert gas atmosphere, heating to 400 ℃, preserving heat for 2 hours and cooling to room temperature to obtain a biochar material;
mixing the biochar material with a KOH solution for reaction and then drying; and
and (3) putting the dried solid substance in an inert gas atmosphere, heating to 600 ℃, preserving the heat for 2h, cooling, washing and drying.
Wherein the weight ratio of the biochar material to the KOH solution is 1: (2-4), wherein the mass concentration of the KOH solution is 4 mol/L.
Example 5
g-C3N4/C/Fe2O3The preparation method of the composite photocatalyst comprises the following steps:
crushing waste leather scraps of a leather factory into 40-mesh leather powder, adding 15g of the leather powder and 300mL of deionized water into a three-necked bottle, and soaking for 12 hours; after 20g of ferric sulfate is completely dissolved in 150mL of water, adding into a three-neck bottle; placing the three-necked bottle in a water bath kettle at 30 ℃ and continuously stirring, soaking for 1h, immediately adjusting the pH of the tanning solution to 2.0 by using a saturated sodium bicarbonate solution, and continuously and slowly adding the saturated sodium bicarbonate solution after 4h to adjust the pH of the tanning solution to 4.0; and then heating a water bath kettle to 40 ℃, continuously soaking the three-mouth bottle in water bath for 2h, and finally washing the tanned hide powder with water and ethanol alternately to obtain a first intermediate.
Adding 15g of the first intermediate and 300mL of deionized water into a three-necked bottle, and soaking for 12 hours; adding 0.45g of sodium formate with the mass percentage concentration of 2% and 0.15g of saturated sodium bicarbonate into a three-necked bottle, putting the three-necked bottle into a 35 ℃ water bath kettle, continuously stirring for 1.5h, and adjusting the pH value to 5.0; then adding 1.5g of melamine resin retanning agent, and stirring for 1-2 h; adding 6g of formic acid with the mass percentage concentration of 2 percent, adding 6g of formic acid after 30min every other time, and adjusting the pH value to 3.5-3.8; and finally, washing the tanned hide powder alternately by using deionized water and ethanol, and drying at 40 ℃ to obtain a second intermediate.
Uniformly placing 5g of the second intermediate in an alumina crucible, placing the alumina crucible in a tubular furnace, introducing nitrogen to exhaust air in the tubular furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours; cooling to room temperature to obtain a biochar material; putting the biochar material into a beaker, adding a KOH solution 4mol/L of which the weight is 4 times that of the biochar material, fully stirring for 3 hours, and drying at the temperature of 60 ℃; heating the dried solid to 600 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, preserving the heat for 2h, cooling, washing with water to neutral pH, and drying to obtain g-C3N4/C/Fe2O3And (3) obtaining the product.
Example 6
g-C3N4/C/Fe2O3The preparation method of the composite photocatalyst comprises the following steps:
crushing waste leather scraps of a leather factory into 40-mesh leather powder, adding 15g of the leather powder and 300mL of water into a three-necked bottle, and soaking for 12 hours; completely dissolving 16g of ferric sulfate in 150mL of water, and then adding into a three-neck bottle; placing the three-necked bottle in a water bath kettle at 30 ℃ and continuously stirring, soaking for 1h, immediately adjusting the pH of the tanning solution to 2.0 by using a saturated sodium bicarbonate solution, and continuously and slowly adding the saturated sodium bicarbonate solution after 4h to adjust the pH of the tanning solution to 4.0; and then heating a water bath kettle to 40 ℃, continuously soaking the three-mouth bottle in the water bath for 2 hours, and finally washing the tanned hide powder by using deionized water and ethanol alternately to obtain a first intermediate.
15g of the first intermediate and 300mL of water were added to a three-necked flask and soaked for 12 hours. Adding 0.45g of sodium formate with the mass percentage concentration of 2% and 0.15g of saturated sodium bicarbonate into a three-necked bottle, putting the three-necked bottle into a water bath kettle at the temperature of 40 ℃, continuously stirring for 1.5h, and adjusting the pH value to 5.5; then adding 1.5g of melamine resin retanning agent, and stirring for 2 hours; adding 6g of formic acid with the mass percentage concentration of 2 percent, adding 6g of formic acid after 30min every other time, and adjusting the pH value to 3.8; and finally, washing the tanned hide powder alternately by using water and ethanol, and drying at 40 ℃ to obtain a second intermediate.
Uniformly placing 5g of the second intermediate in an alumina crucible, placing the alumina crucible in a tubular furnace, introducing nitrogen to exhaust air in the tubular furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours; cooling to room temperature to obtain a biochar material; putting the biochar material into a beaker, adding a KOH solution 4mol/L of which the weight is 4 times that of the biochar material, fully stirring for 3 hours, and drying at the temperature of 60 ℃; heating the dried solid to 600 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, preserving the heat for 2h, cooling, washing with water to neutral pH, and drying to obtain g-C3N4/C/Fe2O3And (3) obtaining the product.
Example 7
g-C3N4/C/Fe2O3Preparation of composite photocatalystThe preparation method comprises the following steps:
crushing waste leather scraps of a leather factory into 40-mesh leather powder, adding 15g of the leather powder and 300mL of deionized water into a three-necked bottle, and soaking for 12 hours; after 12g of iron sulfate was completely dissolved in 150mL of water, the solution was added to a three-necked flask. Placing the three-necked bottle in a water bath kettle at 30 ℃ and continuously stirring, soaking for 1h, immediately adjusting the pH of the tanning solution to 2.0 by using a saturated sodium bicarbonate solution, and continuously and slowly adding the saturated sodium bicarbonate solution after 4h to adjust the pH of the tanning solution to 4.0; and then heating a water bath kettle to 40 ℃, continuously soaking the three-mouth bottle in the water bath for 2 hours, and finally washing the tanned leather powder by using deionized water and ethanol alternately to prepare a first intermediate.
Adding 15g of the first intermediate and 300mL of deionized water into a three-mouth bottle, and soaking for 12 hours; adding 0.45g of sodium formate with the mass percentage concentration of 2% and 0.15g of saturated sodium bicarbonate into a three-necked bottle, putting the three-necked bottle into a 38 ℃ water bath kettle, continuously stirring for 1.5h, and adjusting the pH value to 53; then adding 1.5g of melamine resin retanning agent, and stirring for 1.5 h; adding 6g of formic acid with the mass percentage concentration of 2 percent, adding 6g of formic acid after 30min every other time, and adjusting the pH value to 3.6; and finally, washing the tanned hide powder alternately by using deionized water and ethanol, and drying at 40 ℃ to obtain a second intermediate.
Uniformly placing 5g of the second intermediate in an alumina crucible, placing the alumina crucible in a tubular furnace, introducing nitrogen to exhaust air in the tubular furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours; cooling to room temperature to obtain a biochar material; putting the biochar material into a beaker, adding a KOH solution 4mol/L of which the weight is 4 times that of the biochar material, fully stirring for 3 hours, and drying at the temperature of 60 ℃. Heating the dried solid to 600 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, preserving the heat for 2h, cooling, washing with water to neutral pH, and drying to obtain g-C3N4/C/Fe2O3And (3) obtaining the product.
Test examples
With g-C3N4/C/Fe2O3(0.1)，g-C3N4/C/Fe2O3(0.08)，g-C3N4/C/Fe2O3(0.06) represents the composite photocatalysts prepared in examples 5 to 7, respectively.
(1) SEM characterization
FIG. 1 (a) is pure g-C3N4SEM picture of (a), (b) is g-C of example 53N4/C/Fe2O3SEM photograph of (0.1), (C) and (d) are g-C of example 53N4/C/Fe2O3(0.1) mapping of iron element, from which it can be seen that (b) is specific to (a) g-C of the layered structure3N4The photocatalyst has more hole structures, so that the contact area of the photocatalyst and pollutants is greatly increased; (c) and (d) shows that the iron element is loaded in g-C very uniformly3N4/C/Fe2O3(0.1).
(2) BET characterization
FIG. 2 is a BET plot of pure graphite phase carbon nitride and products of examples 5-7 of the present invention, as seen in FIG. 2, g-C3N4/C/Fe2O3BET of the material is pure g-C3N46 to 10 times of the amount of the compound, that is, g-C prepared by the example of the present invention3N4/C/Fe2O3The specific surface area of the composite photocatalyst is obviously improved.
(3) XPS characterization
FIG. 3 is an XPS plot of pure graphite phase carbon nitride and a product of inventive example 5, where (a) is pure g-C3N4And example 5g-C3N4/C/Fe2O3(0.1) XPS survey of (b) g-C for example 53N4/C/Fe2O3(0.1) high resolution XPS plot. As can be seen from the full spectrum of FIG. 3, g-C3N4And g-C3N4/C/Fe2O3C, N, O in (0.1), and g-C3N4/C/Fe2O3(0.1) also contains Fe, as clearly seen from the high resolution chart, illustrating g-C prepared in the examples of the present invention3N4/C/Fe2O3Successfully compounding the composite photocatalyst material.
(4) Characterization of XRD
FIG. 4 is an XRD pattern of pure graphite phase carbon nitride and products of examples 5 to 7 of the present invention, and it can be seen from the XRD pattern that g-C is obtained when 2 θ =13.1 ° and 27.4 °3N4There are two characteristic peaks corresponding to the (100), (002) crystal planes. g-C3N4 /C/Fe2O3In, Fe2O3The g-C prepared by the examples of the present invention is further illustrated by the crystallographic features (104), (110), (202), (116), (122), (214), etc3N4/C/Fe2O3The composite photocatalyst material is successfully compounded.
(5) DRS characterization and forbidden bandwidth calculation
FIG. 5 is a DRS diagram and a forbidden band diagram of pure graphite-phase carbon nitride and products of examples 5 to 7 of the present invention, which are g-C from FIG. 5(a)3N4And g-C3N4/C/Fe2O3Can see g-C3N4/C/Fe2O3The light absorption capacity is stronger, and the light utilization rate is improved; (b) middle g-C3N4/C/Fe2O3Forbidden band width and g-C3N4Compared with the prior art, the increase of 0.04ev indicates that the forbidden bandwidth of the graphite phase carbon nitride is not affected after the compounding.
(6) PL characterization of fluorescence spectra
FIG. 6 is a PL diagram of pure graphite phase carbon nitride and products of examples 5-7 of the present invention, and it can be seen from FIG. 6 that g-C3N4/C/Fe2O3The recombination rate of the photogenerated electrons and holes is far lower than that of the single g-C3N4That is to say g-C prepared by the examples of the invention3N4/C/Fe2O3The composite photocatalyst obviously reduces the recombination rate of photo-generated electron-hole pairs.
（7）g-C3N4/C/Fe2O3Activity test of composite photocatalyst
For pure graphite phase carbon nitride and g-C prepared in examples 5-7, respectively3N4/C/Fe2O3Performing activity test on the composite photocatalyst, wherein the target pollutant is Cr (VI) solution, and performing activity testThe experimental conditions were as follows:
the initial concentration of the Cr (VI) solution is 20 mg/L, the dosage is 50mL, the dosage of the catalyst is 0.05 g, and a 500W xenon lamp is used as a light source. In the test process, the catalyst and the Cr (VI) solution are stirred for 30min under the dark condition, after the adsorption-desorption balance is achieved, a light source is turned on for photocatalytic reaction, samples are taken every 10 min, the samples are filtered to obtain samples, and the concentration of the Cr (VI) solution is measured by adopting a national standard method. Through Ct/C0The effect of reduction of the Cr (VI) solution was evaluated. Wherein C is0Is the initial concentration of Cr (VI) solution, CtThe concentration of the Cr (VI) solution at the reaction time t is shown. The results are shown in FIG. 7.
From FIG. 7, g-C can be seen3N4/C/Fe2O3Composite catalyst compared with pure g-C3N4Has good effect of photocatalytic reduction of Cr (VI) solution, wherein g-C3N4/C/Fe2O3(0.1) the effect is the best.
（8）g-C3N4/C/Fe2O3Cycling test of composite photocatalyst
The cycling test conditions were the same as the activity test conditions in (7), one cycle was performed every 90 min, and the photocatalyst was directly recovered after each cycle for the next cycle of the test, which was performed for a total of 5 cycles, and the results are shown in fig. 8. As can be seen from FIG. 8, five times of cycle experiments show that the photocatalytic effect of the composite material is not attenuated basically and the stability is good.
As can be seen from the above experimental results, g-C prepared by the examples of the present invention3N4/C/Fe2O3The graphite phase carbon nitride in the composite photocatalyst is firmly loaded in the porous charcoal material, and the composite photocatalyst is not attenuated after five times of cycle tests and has good stability; meanwhile, the contact area of the photocatalyst and the pollutants is greatly increased, the low recombination rate of the photo-generated electron-hole pairs is obviously reduced, and the pollutant treatment capacity can be obviously improved.
In summary, any combination of the various embodiments of the present invention without departing from the spirit of the present invention should be considered as the disclosure of the present invention; within the scope of the technical idea of the invention, any combination of various simple modifications and different embodiments of the technical solution without departing from the inventive idea of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1.g-C3N4/C/Fe2O3The preparation method of the composite photocatalyst is characterized by comprising the following steps:
tanning the leather collagen fibers with iron salt to obtain a first intermediate;
retanning the first intermediate and melamine resin to obtain a second intermediate; and
the second intermediate is calcined under an inert gas atmosphere.
2. The method of claim 1, wherein the method of tanning hide collagen fibers with an iron salt comprises:
soaking the collagen fibers in water;
dissolving ferric salt in water, and adding the dissolved ferric salt into the soaked collagen fiber solution to obtain a first mixed solution; and
the pH of the first mixed solution is adjusted.
3. The method of claim 2, wherein the adjusting the pH of the first mixed solution is by: the pH value of the first mixed solution is adjusted to 2.0 by using a saturated sodium bicarbonate solution, and after 4 hours, the pH value of the first mixed solution is slowly adjusted to 4.0 by using the saturated sodium bicarbonate solution.
4. The method of any one of claims 1 to 3, wherein the mass ratio of the collagen fibers to the iron salt is 1: (0.75 to 1.5).
5. The method of claim 1, wherein the weight ratio of the first intermediate to the melamine resin is (5-10) on a dry basis: 1.
6. the method of claim 1, wherein the method of retanning the first intermediate with a melamine resin comprises:
soaking the first intermediate with deionized water;
adjusting the pH value of the mixed solution of the first intermediate and water;
adding melamine resin into the mixed solution with the adjusted pH value to react to obtain a second mixed solution;
adjusting the pH value of the second mixed solution; and
and washing and drying the collagen fibers in the second mixed solution after the pH value is adjusted.
7. The method of claim 6, wherein the adjusting the pH of the first intermediate and water mixed solution is performed by:
and adding a saturated sodium bicarbonate solution and a sodium formate solution with the mass percentage concentration of 2% into the mixed solution of the first intermediate and the water, stirring for 1.5h at the temperature of 35-40 ℃, and adjusting the pH value to 5.0-5.5.
8. The method of claim 6, wherein the adjusting the pH of the second mixed solution is by: and adding 2% by mass of formic acid into the second mixed solution, and adjusting the pH value to 3.5-3.8.
9. The method of claim 1, wherein the calcining of the second intermediate under an inert gas atmosphere is carried out in two stages, the method comprising:
placing the second intermediate in an inert gas atmosphere, heating to 400 ℃, preserving heat for 2 hours and cooling to room temperature to obtain a biochar material;
mixing the biochar material with a KOH solution for reaction and then drying; and
and (3) putting the dried solid substance in an inert gas atmosphere, heating to 600 ℃, preserving the heat for 2h, cooling, washing and drying.
10. g-C prepared by the method of any one of claims 1 to 93N4/C/Fe2O3A composite photocatalyst is provided.
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