CN109126683A - A kind of modified C3N4The preparation method of material - Google Patents
A kind of modified C3N4The preparation method of material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 230000010355 oscillation Effects 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000005119 centrifugation Methods 0.000 claims description 15
- 238000007792 addition Methods 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 2
- 239000011229 interlayer Substances 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- -1 graphite alkenes Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 241000446313 Lamella Species 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 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
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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 present invention relates to a kind of preparation method fields of composite material, and in particular to a kind of modified C3N4The preparation method field of material.The present invention increases interlamellar spacing, makes Fe by introducing oxygen-containing functional group3+Easily enter g-C3N4Interlayer is adsorbed with the effect of material surface oxygen-containing functional group.It is calcined using under the conditions of nitrogen protection, not only makes ferropexy in material surface, reach good compound, while being g-C3N4Hetero-junctions is provided, makes material by illumination, generates light induced electron and shift rapidly, avoid light induced electron and hole-recombination loses photocatalysis efficiency.With g-C3N4The metal ion quantity of compound use is considerably less, therefore this preparation method is highly suitable for the composite material of noble metal.
Description
Technical field
The present invention relates to a kind of preparation method fields of composite material, and in particular to a kind of modified C3N4The preparation side of material
Method field.
Background technique
C in class graphite carboritride3N4Ring, which interconnects to extend, is extended to a two-dimensional surface, is replaced with n- hetero atom
In the graphite frame containing p conjugated system, the distance of 0.326 nm is kept between the two layers.Because it has unique object
Physicochemical property, g-C3N4Various fields have been widely used in it, such as photocatalysis field, adsorbing domain, sensor and chemical substance
Template.g-C3N4The semiconductor material that suitable band gap is had as one, photon energy is greater than photocatalysis in visible-range
Agent g-C3N4Band gap, light excitation occurs, electronics transits to conduction band (CB) from the generation transition in valence band (VB), forms electronics-
Hole pair, electronics, hole may be in g-C3N4Internal or surface recombination, such as without electronics, hole capture agent, the energy of deposit is at once
It will consume, select trapping agent trapped electron appropriate or hole, it is compound to be suppressed, promote redox reaction hair
It is raw.It has broad application prospects in photocatalysis and hydrogen preparation field, therefore C3N4It is corresponding research be concerned.
Currently, C3N4Using existing following problems:
Problem 1: visible light utilization efficiency is low.Class graphite carboritride C3N4Distinct issues are exactly such material visible the most
Photocatalysis efficiency under the conditions of light is low, and this severely limits further applying for such material.For this problem, carry out big
Quantifier elimination, improves the visible light utilization efficiency of such material, and main mode is to pass through C3N4It is compound with metal and its oxide
It is modified.
Problem 2: C3N4Lack effective complex method with metal oxide.Existing g-C3N4Method of modifying is all will be golden
Category, metal oxide, noble metal and g-C3N4It is doped, or even is only simply mixed.Although the material after compound
Response in visible light region enhances, but mainly metal, metal oxide, noble metal and g-C3N4Spectrum stack result, could not
Achieve the effect that composite modified, g-C cannot be made3N4It is effectively superimposed with dopant photocatalysis band gap, it is difficult to fundamentally improve it
To the absorbability of visible light.
Problem 3: metal and its oxide particle are big, it is difficult to formation and g-C3N4On the one hand the crystal face to match causes big absolutely
Most metals and its oxide can not be with g-C3N4Progress is effectively compound, causes to waste, especially in noble metal and g-C3N4It is compound to change
Property aspect be especially apparent；On the other hand, metal and its oxide and g-C3N4Between insufficient contact, lack fast transfer channel,
Seriously affect catalytic effect.
Problem 4: g-C3N4Theoretically graphite alkenes monolithic layer structure, but a large amount of XRD detection shows that it is mainly class
The multi-ply layer Structural assignments of graphite, this seriously affect the catalyst sufficiently in recent years, monatomic catalysis with
Its unique performance, is concerned.But monatomic or molecule preparation method is complex, obtains the monatomic or single of low cost
Molecular catalyst is more difficult.
Problem 5: in recent years, monatomic catalysis is concerned with its unique performance.But monatomic or molecule preparation side
Method is complex, and the monatomic or monomolecular catalytic agent for obtaining low cost is more difficult.
Summary of the invention
Above-mentioned existing modification there are aiming at the problem that, the present invention by initial oxidation adsorb, afterwards calcine in the way of to g-C3N4Into
Row is modified, and the technology of the present invention design has a characteristic that
Feature 1:The present invention introduces oxygen-containing functional group by oxidation, increases g-C3N4Adsorption capacity and improve its dispersibility.Oxidation
Afterwards, g-C3N4It is upper containing various oxygen-containing functional groups (such as :-OH ,-COOH ,-C=O), original lamellar structure part is stripped,
Specific surface area can be used to increase, while also providing corresponding adsorption site for material, reinforcing material absorption property, and it is oxygen-containing
Functional group also promotes material hydrophilic, makes more g-C3N4It is easily dispersed.
Feature 2:Using material surface oxygen-containing functional group, realize for Fe3+Absorption, form quasi- monatomic effectively connect
It connects.After adsorbing iron ion, original lamella is further stripped, and increases specific surface area.
Feature 3:It is adsorbed in g-C3N4Surface iron atoms are calcined through nitrogen protection, in g-C3N4Magnetisable material is formed, simultaneously
Also to provide corresponding hetero-junctions i.e. unoccupied orbital and fast transfer channel, and then improve catalytic effect.
In order to achieve the object of the present invention, the present invention adopts the following technical scheme:
Step 1: it weighs 25g urea and is put into crucible, the crucible equipped with urea is transferred in Muffle furnace, setting Muffle furnace heating
Rate is 2.3 DEG C of min-1, it is warming up to 550 ~ 600 DEG C of constant temperature, after constant temperature 2h, it is spare that cooling down to room temperature takes out sample A；
Step 2: according to 10g K2Cr2O7The dense H of 50ml 98% is added2SO4Proportional arrangement at oxidation solution B, aoxidized according to 100mL
The ratio of 5-10g sample A is added in liquid B, and sample A is added in oxidation solution B and obtains solution C, at room temperature under the conditions of ultrasonic wave added
After stirring 0.5-5h；Solution C is instilled in 10 times of solution C volume of deionized water, is cooled to room temperature, is removed by centrifugation
Liquid obtains solution W after cleaning solid to neutrality using deionized water；According to this step sample A mass be added into solution W
The FeCl of 0.5-2mol/L is added3Solution, the ratio of addition are the FeCl that 0.1-1mL0.5-2mol/L is added in 1mg sample A3It is molten
Liquid；Obtained suspension is labeled as suspension D；By suspension D to water-bath constant temperature oscillator in 45 DEG C of constant temperature oscillation 2-12h, from
The heart, removed solution are solution E, and solid is solid W；
Step 3: the deionized water of 1-5 solution E volume being added into solid W, vibrates 0.1-0.5 h, centrifugation；It is backward to remove solution
The FeCl with the isometric 0.1-1mol/L of solution E is added in solid3Solution, by suspension to water-bath constant temperature oscillator at 45 DEG C
Constant temperature oscillation 2-12h, centrifugation repeat this step aforesaid operations 1-3 times；After finally 0.1-0.5 h being vibrated in deionized water
Solid freeze-drying obtained, obtained solid matter are labeled as presoma F after centrifuge separation；
Step 4: presoma F is calcined under the conditions of nitrogen protection, and heating rate is 5 DEG C of min-1；After 400-550 DEG C of constant temperature 2h
It is cooled to room temperature, obtains modified C3N4Material.
Technology explanation
Technology illustrates in 1, step 2 for C3N4Carry out oxidation processes,Aoxidize purpose 1It is to increase C3N4Hydroxyl, carboxyl etc. it is oxygen-containing
Its hydrophily improves in functional group；Aoxidize purpose 2It is to increase C3N4The oxygen-containing functional groups such as hydroxyl, carboxyl, improve absorption iron ion
Ability；Aoxidize purpose 3Enhance C3N4Dispersibility, obtain C3N4Block objects are formed by for lamella accumulation, are aoxidized by hypervelocity
Oxygen-containing functional group is introduced on lamella, lamella is stripped, and increases specific surface area, enhances its dispersibility.
Technology illustrates to aoxidize C in order to prevent in 2, step 23N4Agglomeration, takes following measures: solution C is instilled solution C
In the deionized water that 10 times of volume, on the one hand by strong acid dilution, convenient for centrifugation；On the other hand experiment shows containing oxidation C3N4
Strong acid liquid enter its C in aqueous solution3N4Dispersion performance significantly improves, convenient for cleaning.
In addition, aoxidizing C in order to prevent3N4This step of agglomerating is not dried, but is directly entered FeCl after cleaning3It is molten
Liquid is adsorbed.
Technology illustrate 3, step 3 and 2: carried out using chemisorption mode it is compound, be improve composite product performance pass
Key.Chemisorption is realized using the interaction of functional group and metal ion, and " monatomic suction theoretically may be implemented
It is attached "；It can sufficiently avoid metal ion locally to reunite in an experiment, realize metal ion being uniformly distributed on the adsorbent material.
For this step by the way of multiple absorption-cleaning, main purpose is to avoid the occurrence of physical absorption as far as possible and wrap up in miscellaneous
Metal ion.It physical absorption and wraps up in the miscellaneous localized metallic amount that will lead to and increases, later period calcining is easy to generate the metallic particles of bulky grain,
And and C3N4Interaction it is insufficient, influence composite effect.
Spectroscopy detection (Fig. 4) shows that ferro element is evenly distributed in composite material surface；High-resolution TEM(Fig. 3) it is shown in C3N4
The size of the magnetic-particle on surface is nanoscale.
Technology illustrates 4:400-550 DEG C of 4, step constant temperature 2h, and the iron ion of absorption can be made to be converted into magnetic particle first,
The visible light catalytic performance of raising material simultaneously can be with magnetic recovery；Secondly C at this temperature3N4Stable structure will not decompose；Again this
Temperature is conducive to remove unadsorbed corresponding functional group, improves C3N4Performance.
Under the conditions of nitrogen protection, unadsorbed corresponding functional group is assisted in removing, prevents these functional groups from further aoxidizing,
Influence C3N4Performance.
Technology illustrates 5, according to XRD(Fig. 1), C in step 23N4After being oxidized, diffraction maximum is only that intensity decreases, this
Show that layer structure still exists.But after adsorbing iron, diffraction maximum disappears, this shows C3N4Independent sheet is converted by layer structure
Structure, this will significantly increase the specific surface area of material, and then improve absorption and catalytic performance.
Technology illustrates that ultrasound makes g-C in 6, step3N4It is evenly dispersed, it is conducive to Fe3+Into piece at structure among；Using freezing
It is dry to be conducive to retain the biggish specific surface area of raw material, it lays a good foundation for adsorption photochemical catalysis target substance.
The utility model has the advantages that
1, the present invention increases interlamellar spacing, makes Fe by introducing oxygen-containing functional group3+Easily enter g-C3N4Interlayer contains with material surface
The effect of oxygen functional group is adsorbed.
2, it is calcined using under the conditions of nitrogen protection, not only makes ferropexy in material surface, reach good compound, simultaneously
For g-C3N4Hetero-junctions is provided, makes material by illumination, generates light induced electron and shift rapidly, avoid light induced electron and sky
The compound forfeiture photocatalysis efficiency in cave.
3, metal ion solution used in present study can adjust concentration and follow by way of adding metal ion
Ring uses；With g-C3N4The metal ion quantity of compound use is considerably less, therefore this preparation method is highly suitable for answering for noble metal
Condensation material.
Figure of description
Fig. 1 embodiment 6 is modified g-C3N4Transmission plot.
6 g-C of Fig. 2 embodiment3N4With the XRD diagram of modified modification.
6 g-C of Fig. 3 embodiment3N4With the infrared spectrogram of modified modification.
Fig. 4 embodiment 6 is modified g-C3N4Scan energy spectrum diagram.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
A kind of modified C3N4The preparation method of material:
Step 1: it weighs 25g urea and is put into crucible, the crucible equipped with urea is transferred in Muffle furnace, setting Muffle furnace heating
Rate is 2.3 DEG C of min-1, it is warming up to 550 ~ 600 DEG C of constant temperature, after constant temperature 2h, it is spare that cooling down to room temperature takes out sample A；
Step 2: according to 10g K2Cr2O7The dense H of 50ml 98% is added2SO4Proportional arrangement at oxidation solution B, aoxidized according to 100mL
The ratio of 5-10g sample A is added in liquid B, and sample A is added in oxidation solution B and obtains solution C, at room temperature under the conditions of ultrasonic wave added
After stirring 0.5-5h；Solution C is instilled in 10 times of solution C volume of deionized water, is cooled to room temperature, is removed by centrifugation
Liquid obtains solution W after cleaning solid to neutrality using deionized water；According to this step sample A mass be added into solution W
The FeCl of 0.5-2mol/L is added3Solution, the ratio of addition are the FeCl that 0.1-1mL0.5-2mol/L is added in 1mg sample A3It is molten
Liquid；Obtained suspension is labeled as suspension D；By suspension D to water-bath constant temperature oscillator in 45 DEG C of constant temperature oscillation 2-12h, from
The heart, removed solution are solution E, and solid is solid W；
Step 3: the deionized water of 1-5 solution E volume being added into solid W, vibrates 0.1-0.5 h, centrifugation；It is backward to remove solution
The FeCl with the isometric 0.1-1mol/L of solution E is added in solid3Solution, by suspension to water-bath constant temperature oscillator at 45 DEG C
Constant temperature oscillation 2-12h, centrifugation repeat this step aforesaid operations 1-3 times；After finally 0.1-0.5 h being vibrated in deionized water
Solid freeze-drying obtained, obtained solid matter are labeled as presoma F after centrifuge separation；
Step 4: presoma F is calcined under the conditions of nitrogen protection, and heating rate is 5 DEG C of min-1；After 400-550 DEG C of constant temperature 2h
It is cooled to room temperature, obtains modified C3N4Material.
Embodiment 2
A kind of modified C3N4The preparation method of material, the present embodiment is substantially the same manner as Example 1, the difference is that: step 4
In, it is cooled to room temperature after 400-550 DEG C of constant temperature 2h, preferably, is cooled to room temperature after 400 DEG C of constant temperature 2h.
Technology explanation: iron generates α phase oxidation iron at 400 DEG C, significantly improves the magnetic recovery performance of product, saturated magnetization
Intensity is greater than 20 emu/g.
Embodiment 3
A kind of modified C3N4The preparation method of material, the present embodiment is essentially identical with embodiment 1 or 2, the difference is that: step
Corresponding portion is changed to that the FeCl of 2mol/L is added into solution W according to this step sample A mass be added in 23Solution, addition
Ratio be 1mg sample A be added 0.1mL2mol/L FeCl3Solution；Obtained suspension is labeled as suspension D；It will be suspended
Liquid D is to water-bath constant temperature oscillator in 45 DEG C of constant temperature oscillation 12h.
Technology explanation: experimental study shows the present embodiment middle and high concentration iron, is conducive to the quick adsorption of iron ion, C3N4Material
Material is easily peeled off, but high concentration ferrous solution solution occur flocculation package phenomenon, 45 DEG C of constant temperature oscillation 12h, longer temperature compared with
Under the conditions of height, can reduce flocculation influences.
Embodiment 4
A kind of modified C3N4The preparation method of material, the present embodiment is essentially identical with embodiment 1 or 2, the difference is that: step
Corresponding portion is changed to that the FeCl of 0.8mol/L is added into solution W according to this step sample A mass be added in 23Solution adds
The ratio added is the FeCl that 0.5mL0.8mol/L is added in 1mg sample A3Solution；Obtained suspension is labeled as suspension D；It will
Suspension D is to water-bath constant temperature oscillator in 45 DEG C of constant temperature oscillation 4h.
Technology explanation: by adjusting parameter, combined coefficient is improved.
Embodiment 5
A kind of modified C3N4The preparation method of material, the present embodiment and embodiment 1 or 2 or 3 or 4 are essentially identical, and difference exists
It is changed to the middle deionized water that 3 solution E volumes are added into solid W in step 3 corresponding portion, vibrates 0.5 h, centrifugation；Removal
The FeCl with the isometric 0.3mol/L of solution E is added after solution into solid3Solution, by suspension to water-bath constant temperature oscillator
In 45 DEG C of constant temperature oscillation 2h, centrifugation is repeated this step aforesaid operations 3 times.
Embodiment 6
A kind of modified C3N4The preparation method of material, the present embodiment and embodiment 1 or 2 or 3 or 4 are essentially identical, and difference exists
The FeCl that 0.8mol/L is added into solution W for the sample A mass be added according to this step is changed in step 2 corresponding portion3It is molten
Liquid, the ratio of addition are the FeCl that 0.5mL0.8mol/L is added in 1mg sample A3Solution；Obtained suspension is labeled as suspension
D；By suspension D to water-bath constant temperature oscillator in 45 DEG C of constant temperature oscillation 4h；
The deionized water of 3 solution E volumes is added in step 3 into solid W, vibrates 0.5 h, centrifugation；To solid after removal solution
Middle addition and the isometric FeCl of solution E3Solution, by suspension to water-bath constant temperature oscillator in 45 DEG C of constant temperature oscillation 2h, from
The heart repeats this step aforesaid operations 3 times, the FeCl of 3 additions3Solution concentration be followed successively by 0.5mol/L, 0.2mol/L and
0.1mol/L。
Technology explanation: 50 mg sewage treating material F, it 2 hours can be under visible light conditions, for 50 mL, 20 mg/L
The removal rate of methyl orange is 92% or more, and saturation magnetization is greater than 34 emu/g.It can magnetic recovery.
Claims (6)
1. a kind of modified C3N4The preparation method of material:
Step 1: it weighs 25g urea and is put into crucible, the crucible equipped with urea is transferred in Muffle furnace, setting Muffle furnace heating
Rate is 2.3 DEG C of min-1, it is warming up to 550 ~ 600 DEG C of constant temperature, after constant temperature 2h, it is spare that cooling down to room temperature takes out sample A；
Step 2: according to 10g K2Cr2O7The dense H of 50ml 98% is added2SO4Proportional arrangement at oxidation solution B, according to 100mL oxidation solution
The ratio of 5-10g sample A is added in B, and sample A is added in oxidation solution B and obtains solution C, is stirred under the conditions of ultrasonic wave added at room temperature
After mixing 0.5-5h；Solution C is instilled in 10 times of solution C volume of deionized water, is cooled to room temperature, liquid is removed by centrifugation
Body obtains solution W after cleaning solid to neutrality using deionized water；Added according to this step sample A mass be added into solution W
Enter the FeCl of 0.5-2mol/L3Solution, the ratio of addition are the FeCl that 0.1-1mL0.5-2mol/L is added in 1mg sample A3Solution；
Obtained suspension is labeled as suspension D；By suspension D to water-bath constant temperature oscillator in 45 DEG C of constant temperature oscillation 2-12h, it is centrifuged,
Removed solution is solution E, and solid is solid W；
Step 3: the deionized water of 1-5 solution E volume being added into solid W, vibrates 0.1-0.5 h, centrifugation；It is backward to remove solution
The FeCl with the isometric 0.1-1mol/L of solution E is added in solid3Solution, by suspension to water-bath constant temperature oscillator at 45 DEG C
Constant temperature oscillation 2-12h, centrifugation repeat this step aforesaid operations 1-3 times；After finally 0.1-0.5 h being vibrated in deionized water
Solid freeze-drying obtained, obtained solid matter are labeled as presoma F after centrifuge separation；
Step 4: presoma F is calcined under the conditions of nitrogen protection, and heating rate is 5 DEG C of min-1；It is dropped after 400-550 DEG C of constant temperature 2h
It warms to room temperature, obtains modified C3N4Material.
2. a kind of as described in claim 1, modified C3N4The preparation method of material, it is characterised in that be cooled to after 400 DEG C of constant temperature 2h
Room temperature.
3. a kind of as claimed in claim 1 or 2, modified C3N4The preparation method of material, it is characterised in that according to this step in step 2
The FeCl of 2mol/L is added into solution W for rapid sample A mass be added3Solution, the ratio of addition are 1mg sample A addition
The FeCl of 0.1mL2mol/L3Solution；Obtained suspension is labeled as suspension D；Suspension D to water-bath constant temperature oscillator is existed
45 DEG C of constant temperature oscillation 12h.
4. a kind of as claimed in claim 1 or 2, modified C3N4The preparation method of material, it is characterised in that phase in step 2 in step 2
It should partially be changed to that the FeCl of 0.8mol/L is added into solution W according to this step sample A mass be added3Solution, addition
Ratio is the FeCl that 0.5mL0.8mol/L is added in 1mg sample A3Solution；Obtained suspension is labeled as suspension D；It will be suspended
Liquid D is to water-bath constant temperature oscillator in 45 DEG C of constant temperature oscillation 4h.
5. a kind of as claimed in claim 1 or 2 or 3 or 4, modified C3N4The preparation method of material, it is characterised in that in step 3 to
The deionized water of 3 solution E volumes is added in solid W, vibrates 0.5 h, centrifugation；Remove solution after into solid be added and solution E
The FeCl of isometric 0.3mol/L3Solution is centrifuged by suspension to water-bath constant temperature oscillator in 45 DEG C of constant temperature oscillation 2h, weight
Duplicate step aforesaid operations 3 times.
6. a kind of as claimed in claim 1 or 2 or 3 or 4, modified C3N4The preparation method of material, it is characterised in that according to this step
The FeCl of 0.8mol/L is added into solution W for sample A mass be added3Solution, the ratio of addition are 1mg sample A addition
The FeCl of 0.5mL0.8mol/L3Solution；Obtained suspension is labeled as suspension D；By suspension D to water-bath constant temperature oscillator
In 45 DEG C of constant temperature oscillation 4h；
The deionized water of 3 solution E volumes is added in step 3 into solid W, vibrates 0.5 h, centrifugation；To solid after removal solution
Middle addition and the isometric FeCl of solution E3Solution, by suspension to water-bath constant temperature oscillator in 45 DEG C of constant temperature oscillation 2h, from
The heart repeats this step aforesaid operations 3 times, the FeCl of 3 additions3Solution concentration be followed successively by 0.5mol/L, 0.2mol/L and
0.1mol/L。
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