CN109126683B - Modified C3N4Method for producing a material - Google Patents
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- 229910052742 iron Inorganic materials 0.000 abstract description 11
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
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- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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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
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention relates to the field of preparation methods of composite materials, in particular to a modified C3N4The field of preparation methods of materials. The invention increases the interlayer spacing by introducing oxygen-containing functional groups to enable Fe3+Easy access to g-C3N4The interlayer and the oxygen-containing functional group on the surface of the material act for adsorption. The iron is fixed on the surface of the material by calcining under the protection of nitrogen, so that good compounding is achieved, and the iron is g-C3N4The heterojunction is provided, so that the material generates photo-generated electrons to be rapidly transferred when being illuminated, and the phenomenon that the photo-generated electrons and holes are compounded to lose photocatalysis efficiency is avoided. And g-C3N4The quantity of the metal ions used for compounding is very small, so the preparation method is very suitable for the composite material of the noble metal.
Description
Technical Field
The invention relates to the field of preparation methods of composite materials, in particular to a modified C3N4The field of preparation methods of materials.
Background
C in graphite-like carbon nitrogen compound3N4The rings are connected to each other, extended to a two-dimensional plane, substituted with n-heteroatoms in a graphite framework containing a p-conjugated system, maintaining a distance of 0.326 nm between the two layers. Because of its unique physicochemical properties, g-C3N4Has been widely used in various fields such as the field of photocatalysis, the field of adsorption, sensors, and chemical templates. g-C3N4As a semiconductor material with a proper band gap, the photon energy is larger than that of the photocatalyst g-C in the visible light range3N4The band gap of (A) is excited by light, electrons jump from the Valence Band (VB) to the Conduction Band (CB) to form electron-hole pairs, and the electrons and holes may be in g-C3N4The energy stored in the internal or surface recombination, such as no electron or hole trapping agent, is consumed immediately, and the recombination is inhibited and the redox reaction is promoted by selecting a proper trapping agent to trap the electron or the hole. It has wide application prospect in the fields of photocatalysis and hydrogen production, so C3N4The corresponding research is of great interest.
At present, C3N4The following problems exist with the application:
problem 1: the utilization rate of visible light is low. Graphite-like carbon nitrogen compound C3N4The most prominent problem is the low photocatalytic efficiency of the material under visible light conditions, which severely limits the further application of the material. Aiming at the problem, a great deal of research is carried out to improve the visible light utilization rate of the material, and the main mode is to pass through C3N4And metal and oxide composite modification.
Problem 2：C3N4And the lack of an effective means of complexing the metal oxide. Existing g-C3N4The modification method is to mix metal, metal oxide, noble metal and g-C3N4Doping is performed, even with simple mixing. Although the response of the material after being compounded in a visible light region is enhanced, the materials mainly comprise metal, metal oxide, noble metal and g-C3N4The spectrum superposition result can not achieve the effect of composite modification and can not lead g-C3N4And the doped material has effective superposition with a photocatalytic band gap, so that the absorption capacity of the doped material on visible light is difficult to improve fundamentally.
Problem 3: the metal and its oxide particles are large and difficult to form with g-C3N4The matched crystal faces, on the one hand, cause that most of metals and oxides thereof cannot be matched with g-C3N4Effective compounding is carried out, causing waste, especially in the case of noble metals and g-C3N4The composite modification aspect is particularly obvious; in another aspect, the metals and their oxides with g-C3N4The contact between the catalyst and the catalyst is insufficient, and a rapid transfer channel is lacked, so that the catalytic effect is seriously influenced.
Problem 4：g-C3N4Theoretically, the graphene monolithic layer structure is adopted, but a large number of XRD detections show that the catalyst is mainly arranged in a graphite-like multilayer lamellar structure, which seriously influences the full matching of the catalyst, and in recent years, the single-atom catalyst is paid much attention to by the unique performance thereof. However, the preparation method of the monoatomic or molecular catalyst is complicated, and the preparation of the low-cost monoatomic or molecular catalyst is difficult.
Problem 5: in recent years, monatomic catalysis has received much attention for its unique properties. However, the preparation method of the monoatomic or molecular catalyst is complicated, and the preparation of the low-cost monoatomic or molecular catalyst is difficult.
Disclosure of Invention
Aiming at the problems existing in the prior modification, the invention utilizes the modes of firstly oxidizing, adsorbing and then calcining to react g-C3N4The technical concept of the invention is characterized in that:
the characteristics are as follows:the invention introduces oxygen-containing functional groups through oxidation to increase g-C3N4Adsorption capacity and improved dispersibility. After oxidation, g-C3N4Contains various oxygen-containing functional groups (such as-OH, -COOH and-C = O), the original lamellar structure part is stripped, thereby increasing the available specific surface area, simultaneously providing corresponding adsorption sites for the material, enhancing the adsorption performance of the material, and the oxygen-containing functional groups also improve the hydrophilicity of the material, so that the g-C is higher3N4Easy to disperse.
And (2) the characteristics:the method for preparing Fe by using oxygen-containing functional groups on the surface of the material3+The quasi-monoatomic effective linkage is formed. After the iron ions are adsorbed, the original lamella is further stripped, and the specific surface area is increased.
And (3) characteristics:adsorption to g-C3N4Surface iron atoms, calcining under nitrogen protection at g-C3N4The magnetic substance is formed, and meanwhile, a corresponding heterojunction, namely an empty track, and a rapid transfer channel are provided, so that the catalytic effect is improved.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
step 1: weighing 25g of urea, putting the urea into a crucible, transferring the crucible filled with the urea into a muffle furnace, and setting the temperature rise rate of the muffle furnace to be 2.3 ℃ per minute-1Heating to 550-600 ℃, keeping the temperature constant for 2 hours, cooling to room temperature, and taking out the sample A for later use;
step 2: according to 10g K2Cr2O750ml of 98% strength concentrate are addedH2SO4Preparing an oxidizing solution B, adding a sample A into the oxidizing solution B according to the proportion that 100mL of the oxidizing solution B is added into 5-10g of the sample A to obtain a solution C, and stirring for 0.5-5h at room temperature under the ultrasonic auxiliary condition; dripping the solution C into deionized water with the volume 10 times that of the solution C, cooling to room temperature, removing liquid in a centrifugal mode, and cleaning the solid to be neutral by using the deionized water to obtain a solution W; adding FeCl of 0.5-2mol/L into the solution W according to the mass of the sample A added in the step3The solution is added in a proportion that 1mg of sample A is added with 0.1-1mL0.5-2mol/L FeCl3A solution; marking the obtained suspension as suspension D; oscillating the suspension D in a water bath constant temperature oscillator at the constant temperature of 45 ℃ for 2-12h, and centrifuging to remove the solution E and the solid W;
and step 3: adding deionized water with the volume of 1-5 solution E into the solid W, oscillating for 0.1-0.5 h, and centrifuging; adding FeCl of 0.1-1mol/L with the same volume as the solution E into the solid after removing the solution3Solution, putting the suspension into a water bath constant temperature oscillator, oscillating for 2-12h at the constant temperature of 45 ℃, centrifuging, and repeating the operation for 1-3 times; finally, freezing and drying the solid obtained after the solid is oscillated for 0.1 to 0.5 h in deionized water and then is subjected to centrifugal separation, and marking the obtained solid as a precursor F;
and 4, step 4: calcining the precursor F under the protection of nitrogen, wherein the heating rate is 5 ℃ min-1(ii) a Keeping the temperature at 400-3N4A material.
Description of the technology
Technical description 1, step 2 for C3N4The oxidation treatment is carried out, and the oxidation treatment is carried out,oxidation of object 1Is to increase C3N4A hydroxyl group, a carboxyl group, or the like, to improve the hydrophilicity;oxidation of purpose 2Is to increase C3N4The oxygen-containing functional groups such as hydroxyl, carboxyl and the like improve the iron ion adsorption capacity;oxidation of destination 3Enhancement of C3N4To obtain C3N4In order to stack the blocky objects formed by the sheets, oxygen-containing functional groups are introduced on the sheets through overspeed oxidation, the sheets are peeled off, the specific surface area is increased, and the dispersity is enhanced.
Technical description 2, step 2 for preventing oxidation of C3N4Caking, the following measures are taken: dropping the solution C into deionized water with the volume 10 times that of the solution C, so that on one hand, strong acid liquid is diluted and is convenient to centrifuge; on the other hand, the experiment shows that the catalyst contains oxidized C3N4The strong acid solution enters into the aqueous solution to obtain C3N4The dispersing performance is obviously improved, and the cleaning is convenient.
In addition, to prevent oxidation of C3N4The agglomeration step is not dried, but is directly carried out into FeCl after being cleaned3The solution is adsorbed.
Technical description 3, steps 3 and 2: the chemical adsorption mode is adopted for compounding, which is the key for improving the performance of the compound product. The chemical adsorption is realized by utilizing the interaction of functional groups and metal ions, and the 'monoatomic adsorption' can be realized theoretically; in the experiment, the local agglomeration of metal ions can be fully avoided, and the uniform distribution of the metal ions on the adsorption material is realized. The step adopts a mode of multiple adsorption-cleaning, and the main purpose of the step is to avoid the occurrence of physical adsorption and impurity-coated metal ions as far as possible. Physical adsorption and impurity inclusion can cause the local metal content to increase, and later calcination easily generates large-particle metal particles which are mixed with C3N4The interaction of (2) is insufficient, and the composite effect is influenced.
Energy spectrum detection (figure 4) shows that iron element is uniformly distributed on the surface of the composite material; high resolution TEM (FIG. 1) is shown at C3N4The size of the magnetic particles on the surface is in the nanometer range.
Technical description 4, step 4: the temperature is constant at 550 ℃ for 2h under 400-; second at this temperature C3N4The structure is stable and can not be decomposed; the temperature is favorable for removing the corresponding non-adsorbed functional groups again, and C is increased3N4The performance of (c).
Under the protection of nitrogen, the method helps to remove the corresponding non-adsorbed functional groups and prevent the functional groups from further oxidizing to influence C3N4Property ofCan be used.
Technical description 5, according to XRD (FIG. 2), step 2C3N4After oxidation, the diffraction peaks are only reduced in intensity, indicating that the lamellar structure is still present. However, after adsorption of iron, the diffraction peak disappeared, indicating C3N4The laminated structure is converted into a single sheet structure, so that the specific surface area of the material is greatly increased, and the adsorption and catalysis performances are further improved.
Technical description 6 sonication of g-C in step3N4Uniform dispersion, and is favorable to Fe3+Entering the middle of the sheet forming structure; the adoption of freeze drying is beneficial to keeping larger specific surface area of the raw material, and lays a good foundation for adsorbing the photocatalytic target substance.
Has the advantages that:
1. the invention increases the interlayer spacing by introducing oxygen-containing functional groups to enable Fe3+Easy access to g-C3N4The interlayer and the oxygen-containing functional group on the surface of the material act for adsorption.
2. The iron is fixed on the surface of the material by calcining under the protection of nitrogen, so that good compounding is achieved, and the iron is g-C3N4The heterojunction is provided, so that the material generates photo-generated electrons to be rapidly transferred when being illuminated, and the phenomenon that the photo-generated electrons and holes are compounded to lose photocatalysis efficiency is avoided.
3. The metal ion solution used in the research can be adjusted in concentration for recycling through a mode of supplementing metal ions; and g-C3N4The quantity of the metal ions used for compounding is very small, so the preparation method is very suitable for the composite material of the noble metal.
Drawings
FIG. 1 example 6 modification of g-C3N4Transmission diagram.
FIG. 2 example 6 g-C3N4And a modified XRD pattern.
FIG. 3 example 6 g-C3N4And a modified infrared spectrum.
FIG. 4 example 6 modification of g-C3N4Scanning the energy spectrum.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Modified C3N4The preparation method of the material comprises the following steps:
step 1: weighing 25g of urea, putting the urea into a crucible, transferring the crucible filled with the urea into a muffle furnace, and setting the temperature rise rate of the muffle furnace to be 2.3 ℃ per minute-1Heating to 550-600 ℃, keeping the temperature constant for 2 hours, cooling to room temperature, and taking out the sample A for later use;
step 2: according to 10g K2Cr2O750ml of 98% concentrated H are added2SO4Preparing an oxidizing solution B, adding a sample A into the oxidizing solution B according to the proportion that 100mL of the oxidizing solution B is added into 5-10g of the sample A to obtain a solution C, and stirring for 0.5-5h at room temperature under the ultrasonic auxiliary condition; dripping the solution C into deionized water with the volume 10 times that of the solution C, cooling to room temperature, removing liquid in a centrifugal mode, and cleaning the solid to be neutral by using the deionized water to obtain a solution W; adding FeCl of 0.5-2mol/L into the solution W according to the mass of the sample A added in the step3The solution is added in a proportion that 1mg of sample A is added with 0.1-1mL0.5-2mol/L FeCl3A solution; marking the obtained suspension as suspension D; oscillating the suspension D in a water bath constant temperature oscillator at the constant temperature of 45 ℃ for 2-12h, and centrifuging to remove the solution E and the solid W;
and step 3: adding deionized water with the volume of 1-5 solution E into the solid W, oscillating for 0.1-0.5 h, and centrifuging; adding FeCl of 0.1-1mol/L with the same volume as the solution E into the solid after removing the solution3Solution, putting the suspension into a water bath constant temperature oscillator, oscillating for 2-12h at the constant temperature of 45 ℃, centrifuging, and repeating the operation for 1-3 times; finally oscillating the mixture in deionized water for 0.1 to 0.5 h and then carrying out centrifugal separationFreezing and drying the obtained solid, and marking the obtained solid as a precursor F;
and 4, step 4: calcining the precursor F under the protection of nitrogen, wherein the heating rate is 5 ℃ min-1(ii) a Keeping the temperature at 400-3N4A material.
Example 2
Modified C3N4The material was prepared in the same manner as in example 1, except that: in step 4, the temperature is maintained at 400-550 ℃ for 2h and then cooled to room temperature, preferably, the temperature is maintained at 400 ℃ for 2h and then cooled to room temperature.
Technical description: the alpha-phase iron oxide is generated by iron at 400 ℃, the magnetic recovery performance of the product is obviously improved, and the saturation magnetization is more than 20 emu/g.
Example 3
Modified C3N4The material was prepared in the same manner as in example 1 or 2, except that: the corresponding part in the step 2 is changed into the method that 2mol/L FeCl is added into the solution W according to the mass of the sample A added in the step3Solution, adding FeCl of 0.1mL and 2mol/L into sample A at a ratio of 1mg3A solution; marking the obtained suspension as suspension D; and (4) shaking the suspension D to a water bath constant temperature oscillator at the constant temperature of 45 ℃ for 12 h.
Technical description: experimental research shows that the high-concentration iron in the embodiment is beneficial to the rapid adsorption of iron ions, and C3N4The material is easy to peel off, but the flocculation wrapping phenomenon appears in the high-concentration iron solution, the constant temperature oscillation is carried out for 12 hours at 45 ℃, and the flocculation influence can be reduced under the condition of longer temperature and higher temperature.
Example 4
Modified C3N4The material was prepared in the same manner as in example 1 or 2, except that: the corresponding part in the step 2 is changed into that 0.8mol/L FeCl is added into the solution W according to the mass of the sample A added in the step3Solution, adding FeCl of 0.5mL0.8mol/L in the proportion of 1mg of sample A3A solution; marking the obtained suspension as suspension D; mixing the suspension D toThe water bath constant temperature oscillator is used for oscillating for 4 hours at the constant temperature of 45 ℃.
Technical description: and the synthesis efficiency is improved by adjusting parameters.
Example 5
Modified C3N4The preparation method of the material is basically the same as that of the embodiment 1 or 2 or 3 or 4, except that the corresponding part of the step 3 is changed to add deionized water with the volume of 3 solutions E into the solid W, oscillate for 0.5 h and centrifuge; after the solution is removed, FeCl of 0.3mol/L which is equal to the volume of the solution E is added into the solid3And (3) solution, putting the suspension into a water bath constant temperature oscillator, oscillating for 2 hours at the constant temperature of 45 ℃, centrifuging, and repeating the operation for 3 times.
Example 6
Modified C3N4The material preparation method, this example is substantially the same as that of example 1 or 2 or 3 or 4, except that the corresponding part of step 2 is changed to add FeCl of 0.8mol/L to the solution W according to the mass of the sample A added in this step3Solution, adding FeCl of 0.5mL0.8mol/L in the proportion of 1mg of sample A3A solution; marking the obtained suspension as suspension D; oscillating the suspension D in a water bath constant temperature oscillator at the constant temperature of 45 ℃ for 4 h;
adding deionized water with the volume of 3 solutions E into the solid W in the step 3, oscillating for 0.5 h, and centrifuging; adding FeCl with the same volume as the solution E into the solid after removing the solution3Solution, placing the suspension in a water bath constant temperature oscillator, oscillating at 45 deg.C for 2h, centrifuging, repeating the above operation for 3 times, and adding FeCl for 3 times3The concentration of the solution is 0.5mol/L, 0.2mol/L and 0.1mol/L in sequence.
Technical description: the 50 mg sewage treatment material F can remove 50mL of 20 mg/L methyl orange under visible light conditions within 2 hours, the removal rate is more than 92%, and the saturation magnetization is more than 34 emu/g. Can be recovered magnetically.
Claims (4)
1. Modified C3N4The preparation method of the material comprises the following steps:
step 1: weighing 25g of urea, placing the urea into a crucible, and transferring the crucible filled with the urea to a horseIn the muffle furnace, the temperature rise rate of the muffle furnace is set to be 2.3 ℃ min-1Heating to 550-600 ℃, keeping the temperature constant for 2 hours, cooling to room temperature, and taking out the sample A for later use;
step 2: according to 10g K2Cr2O750mL of 98% concentrated H was added2SO4Preparing an oxidizing solution B, adding a sample A into the oxidizing solution B according to the proportion that 100mL of the oxidizing solution B is added into 5-10g of the sample A to obtain a solution C, and stirring for 0.5-5h at room temperature under the ultrasonic auxiliary condition; dripping the solution C into deionized water with the volume 10 times that of the solution C, cooling to room temperature, removing liquid in a centrifugal mode, and cleaning the solid to be neutral by using the deionized water to obtain a solution P; adding FeCl of 0.5-2mol/L into the solution P according to the mass of the sample A added in the step3The solution is added in a proportion that 1mg of sample A is added with 0.1-1mL0.5-2mol/L FeCl3A solution; marking the obtained suspension as suspension D; placing the suspension D in a water bath constant temperature oscillator, oscillating at 45 deg.C for 2-12h, centrifuging to obtain solution E and solid W;
and step 3: adding deionized water with the volume of 1-5 solution E into the solid W, oscillating for 0.1-0.5 h, and centrifuging; adding FeCl of 0.1-1mol/L with the same volume as the solution E into the solid after removing the solution3Placing the suspension in a water bath constant temperature oscillator, oscillating at 45 deg.C for 2-12h, centrifuging, and repeating the above steps for 1-3 times; finally, freezing and drying the solid obtained after the solid is oscillated for 0.1 to 0.5 h in deionized water and then is subjected to centrifugal separation, and marking the obtained solid as a precursor F;
and 4, step 4: calcining the precursor F under the protection of nitrogen, wherein the heating rate is 5 ℃ min-1(ii) a Keeping the temperature at 400-3N4A material.
2. The modified C as claimed in claim 13N4The preparation method of the material is characterized in that in the step 2, 2mol/L FeCl is added into the solution P according to the mass of the sample A added in the step3Solution, adding FeCl of 0.1mL and 2mol/L into sample A at a ratio of 1mg3A solution; placing the suspension D in a water bath at constant temperatureThe shaker was thermostatically shaken at 45 ℃ for 12 h.
3. The modified C as claimed in claim 13N4The preparation method of the material is characterized in that FeCl of 0.8mol/L is added into the solution P according to the mass of the sample A added in the step 23Solution, adding FeCl of 0.5mL0.8mol/L in the proportion of 1mg of sample A3A solution; and (4) placing the suspension D in a water bath constant temperature oscillator to oscillate for 4h at the constant temperature of 45 ℃.
4. A modified C as claimed in claim 1, 2 or 33N4The preparation method of the material is characterized in that deionized water with the volume of 3 solutions E is added into the solid W in the step 3, the oscillation is carried out for 0.5 h, and the centrifugation is carried out; after the solution is removed, 0.3mol/L FeCl which is equal to the volume of the solution E is added into the solid3And (3) putting the suspension into a water bath constant temperature oscillator, oscillating for 2 hours at the constant temperature of 45 ℃, centrifuging, and repeating the operation for 3 times.
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