CN109107523A - Ultra-thin graphite-phase C3N4/ calcite nanosheet composite material and its preparation method and application - Google Patents
Ultra-thin graphite-phase C3N4/ calcite nanosheet composite material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of ultra-thin graphite-phase C3N4/ calcite nanosheet composite material, the composite material is with ultra-thin graphite-phase C3N4For carrier, the ultra-thin graphite-phase C3N4Supported on carriers has calcite nanometer sheet.The present invention also provides a kind of ultra-thin graphite-phase C3N4The preparation method of/calcite nanosheet composite material, comprising the following steps: (1) prepare ultra-thin graphite-phase C3N4Carrier suspension；(2) by Ca2+Ultra-thin graphite-phase C obtained in solution and step (1)3N4Carrier suspension is uniformly mixed, and ultrasonic treatment obtains mixed solution, then passes to CO2Reaction, centrifugal treating, collects the precipitating ultra-thin graphite-phase C of drying to obtain after the reaction was completed3N4/ calcite nanosheet composite material.Ultra-thin graphite-phase C of the invention3N4/ calcite nanosheet composite material can be absorption Cd2+More active sites are provided, can be greatly improved to Cd in waste water2+Removal rate.
Description
Technical field
The invention belongs to functional composite material absorbent fields more particularly to a kind of for adsorbing the composite wood of cadmium in waste water
Material and preparation method thereof, application.
Background technique
Cadmium is a Heavy Metallic Elements, is more toxic, serious by the air of cadmium pollution and food harm to the human body, and
Human body metabolism is slower.Cadmium will not have potential cumulative bad by the microbial degradation in water body, can in people's cylinder accumulation, from
And cause chronic liver, kidney, nerve and disease of cardiovascular system.Therefore, seek a kind of effective method of green to remove cadmium
It is very important to acceptable level.Currently, absorption is typically considered one of most promising technology, this method can
To be effectively removed soluble and insoluble pollutant, without generating dangerous by-product.
Carbonate is considered as the good material for removing heavy metals in industrial wastewater and fixed metal.Calcium carbonate is in nature
Exist usually in the form of calcite, aragonite, vaterite etc., but under the conditions of normal temperature and pressure, calcite phase is its unique heat
Mechanics stable phase, so, the general calcium carbonate that we synthesize is calcite.Some researchs have shown that Cd (II) can enter side's solution
Stone lattice forms (Cd, Ca) CO3Solid solution, to realize the removal of cadmium.However, since calcite has high-crystallinity and smooth
Surface cause its specific surface area smaller without boundary defect so that adsorption capacity very little of the Cd (II) on calcite, side
Xie Shi cannot be widely used.Therefore, the adsorption capacity for how improving calcite has become the hot topic of research.Increase specific surface
Product is to improve calcite to the effective measures of heavy metal adsorption.China apply for a patent CN106111049A disclose it is a kind of heavy
Metal sewage adsorbs nanocomposite and preparation method thereof, which is changed by the surface of nanometer titanium dioxide and nano kaoline
Property cladding calcite type calcium carbonate, gained composite material 30min is more than 97% to the adsorption rate containing heavy metal containing sewage, and adsorbance reaches
To 5000ug/g, adsorbance is lower.
C3N4It is a kind of carboritride, there is 5 kinds of allotropes, including α phase C3N4, β phase C3N4, quasi- cubic phase C3N4、
Cubic phase C3N4, graphite-phase C3N4(g-C3N4).Wherein, graphite-phase C3N4(g-C3N4) it is five kinds of C3N4Most stable of one kind, by list
The carbonitride thin slice of layer is formed by stacked in multi-layers.Since it is with special electronic structure and band structure, good biology
Compatibility, have to visible light certain absorption, antiacid, alkali, light burn into aqueous solution in high stability and nontoxic, structure and
Performance is easy to the features such as regulating and controlling, thus it has biggish answer in fields such as photocatalysis, the depollution of environment, sensor, pharmaceutical carriers
Use prospect.g-C3N4Interlayer structure has certain interlamellar spacing, theoretically has big specific surface area.
Up to the present, it yet there are no calcite and ultra-thin g-C in the prior art3N4The compound this kind of materials of nanometer sheet
Material, therefore, passes through ultra-thin g-C3N4It is compound with calcite, the specific surface area of calcite is improved, more Cd (II) absorption is increased
Active site is had a vast market foreground with further increasing the removal rate of Cd in waste water (II).
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, one kind is provided
The ultra-thin graphite-phase C that cadmium active adsorption sites are more, cadmium removal rate is high, structural stability is good, load effect is good3N4/ calcite nanometer
Piece composite material, and preparation method is accordingly provided and is applied in the treatment of waste water with it.In order to solve the above technical problems, of the invention
The technical solution of proposition are as follows:
A kind of ultra-thin graphite-phase C3N4/ calcite nanosheet composite material, the composite material is with ultra-thin graphite-phase C3N4For
Carrier, the ultra-thin graphite-phase C3N4Supported on carriers has calcite nanometer sheet.
Above-mentioned ultra-thin graphite-phase C3N4In/calcite nanosheet composite material, it is preferred that the ultra-thin graphite-phase C3N4It carries
On body, the load capacity of calcite nanometer sheet is the 20-40% of carrier quality.Ultra-thin graphite-phase C3N4Load calcite nanometer sheet
Load capacity in 20-40% be it is best, the low active adsorption sites that will cause of load capacity are low, are not enough to suitable adsorbance；Load capacity
It is excessively high to will cause ultra-thin graphite-phase C3N4Reunite, substantially reduces the specific surface area of material.
Above-mentioned ultra-thin graphite-phase C3N4In/calcite nanosheet composite material, it is preferred that the ultra-thin graphite-phase C3N4For
Two-dimensional layer nanometer chip architecture (2D structure), the calcite nanometer sheet are 3D structure.Due to C3N4Middle nitrogen-atoms can be certain
Complexing occurs with calcium ion in degree, once carbonate is close to C3N4Surface forms calcite with calcium binding with regard to spontaneous
Preceding aggressiveness, and carry out being epitaxially-formed 3D hexagonal crystal structures according to the optimal crystal growth pattern of calcite and (test
Scanning electron microscope (SEM) photograph can prove in journey).The calcite nanometer sheet of 3D structure is attached to the ultra-thin graphite-phase C of 2D structure3N4Nanometer
It is grown in piece, is conducive to the growth district for expanding calcite, can be absorption Cd2+More active sites are provided.
As a general technical idea, the present invention also provides a kind of above-mentioned ultra-thin graphite-phase C3N4/ calcite nanometer sheet is multiple
The preparation method of condensation material, comprising the following steps:
(1) ultra-thin graphite-phase C is prepared3N4Carrier suspension；
(2) by Ca2+Ultra-thin graphite-phase C obtained in solution and step (1)3N4Carrier suspension is uniformly mixed, at ultrasound
Reason obtains mixed solution, then passes to CO2Reaction, centrifugal treating, collects the precipitating ultra-thin graphite of drying to obtain after the reaction was completed
Phase C3N4/ calcite nanosheet composite material.
In above-mentioned preparation method, the ultra-thin graphite-phase C3N4For two-dimensional layer nanometer chip architecture, the calcite nanometer sheet
For 3D structure.
In above-mentioned preparation method, it is preferred that prepare ultra-thin graphite-phase C3N4Carrier suspension is the following steps are included: by trimerization
Cyanamide is put into crucible, heats to obtain blocky graphite phase C in Muffle furnace3N4；Blocky graphite phase C is taken again3N4Be scattered in from
In sub- water, through ultrasound, stewing process, it is filtered to remove and remaining is filtered to remove undispersed blocky graphite phase C3N4(only retain super
The well dispersed solution of sound), gained filtrate is ultra-thin graphite-phase C3N4Carrier suspension；Wherein, the blocky graphite phase C3N4
Weight ratio with deionized water is (0.2-0.5): (200-500).By blocky graphite phase C3N4It is placed in polar solvent water at ultrasound
Reason, can be obtained the ultra-thin graphite-phase C of two-dimensional layer3N4Nanometer sheet, and suspending stabilized a very long time can be kept.In addition, water conduct
A kind of green remover, environmental-friendly, charge stripping efficiency is high.Wherein, when Muffle furnace heats, with the heating of 2-6 DEG C/min
Speed is warming up to 500-650 DEG C, keeps stationary temperature 2-4h, is then down to room temperature with identical rate of temperature fall；Ultrasound, stewing process
When, ultrasonic treatment frequency is 30-50KHz (more preferably 40KHz), sonication treatment time 15-20h, time of repose 30-
45min.Above-mentioned technological parameter can guarantee finally obtained ultra-thin graphite-phase C3N4Form and yield, meet subsequent demand.
In above-mentioned preparation method, it is preferred that the Ca2+Solution and ultra-thin graphite-phase C3N4The weight ratio of carrier suspension is
(30-50): (50-70), the Ca2+Ca in solution2+Concentration is 0.1M.Selection above parameter range can guarantee constructed
Calcite is 3D structure, meets performance requirement.
In above-mentioned preparation method, it is preferred that in the step (2), when ultrasonic treatment, ultrasonic treatment frequency is 30-50KHz
(more preferably 40KHz), sonication treatment time 1-2h；When centrifugal treating, centrifugation rate 4000-5000r/min, when centrifugation
Between be 5-15min, centrifugation number be 3-5 times.
In above-mentioned preparation method, it is preferred that in the step (2), be passed through CO2The time of reaction is 12-20h；It is passed through CO2
The mode of reaction is as follows: at 30-35 DEG C, by sonicated obtained mixed solution (i.e. Ca2+Solution and ultra-thin graphite C3N4It carries
Body mixed solution) and equipped with (NH4)2CO3The surface plate of solid is put into together in closed drier, and with sealed membrane by surface
Ware sealing, and aperture (the preferably 3-5 pinhead-sized holes) on sealed membrane；Wherein, (NH4)2CO3The dosage of solid is to guarantee
Its CO volatilized2Amount be calcite needed for CO22-5 times (more preferably 3 times) of dosage.Select (NH4)2CO3Slowly divide
Solution is used as CO2Source, not only can with rate appropriate provide CO2, decompose the NH generated3It also can further stablizing solution
PH.
As a general technical idea, the present invention also provides a kind of above-mentioned ultra-thin graphite-phase C3N4/ calcite nanometer sheet is multiple
The application of condensation material, the application are the Cd for being used to solidify by composite material in water body2+；Solidification process will be the following steps are included: will
The composite material with contain Cd2+Waste liquid is uniformly mixed, and addition aluminium polychloride progress coagulation handles to obtain after reacting a period of time
Flocculent deposit, centrifugation removal flocculent deposit is i.e. completely at Cd2+Solidification process；Wherein, contain Cd when described2+Cd in waste liquid2+Concentration is
When 1-15mg/L, the additive amount of the composite material is 0.2-2.5g/L.
In above-mentioned application, aluminium polychloride is the high charge polymeric rings chain bodily form with structure with Keggin, to water-borne glue
Body and particulate matter have height charge neutrality and bridge linking effect, and can strongly remove micro- Toxic and heavy metal ion, and character is stablized.
It is a kind of inorganic polymer coagulant, is produced by the polymerization of the bridging action and multivalent anions of hydroxide ion
Molecular weight is larger, the higher inorganic polymer water treatment agent of charge.It therefore will be at the aluminium polychloride of the solid solution after absorption
Reason carries out polymeric precipitation, is conducive to Cd2+Processing after absorption prevents secondary pollution or " source remittance " from polluting.
In the present invention, ultra-thin graphite-phase C3N4/ calcite nanosheet composite material can be formed in adsorption process (Cd,
Ca)CO3Solid solution, this is because Ca2+Ionic radiusIt is in close proximity to Cd2+'sAnd their electricity
Sub- configuration is formed and losing outermost electronics from S atom track in a similar way, it is possible to form (Cd, Ca)
CO3Cd can be improved in solid solution2+Adsorption efficiency.
Compared with the prior art, the advantages of the present invention are as follows:
1, ultra-thin graphite-phase C of the invention3N4/ calcite nanosheet composite material, with ultra-thin graphite-phase C3N4For carrier,
Ultra-thin graphite-phase C3N4Calcite nanometer sheet is modified on carrier.Ultra-thin graphite-phase C3N4It is a kind of with high-specific surface area, tool
There is two-dimensional layer nanometer sheet (2D) structure, and calcite nanometer sheet is 3D structure, the present invention for the first time solves the side with 3D structure
Stone is attached to the ultra-thin graphite-phase C of 2D structure3N4It is grown in nanometer sheet, is conducive to the region for expanding calcite growth, can be suction
Attached Cd2+More active sites are provided, can be greatly improved to Cd in waste water2+Removal rate.
2, Cd after the present invention will be adsorbed2+Solution afterwards is handled with aluminium polychloride, is conducive to the taking back and process of Cd in this way,
Secondary pollution or " source remittance " is prevented to pollute.
3, the ultra-thin graphite-phase C that the present invention is prepared3N4/ calcite nanosheet composite material stable structure, is conducive to reality
Border application.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 be embodiment 2 in Related product transmission electron microscope picture (in figure, a be ultra-thin graphite-phase C3N4；B is ultra-thin graphite
Phase C3N4/ calcite nanosheet composite material；C is absorption Cd2+Ultra-thin graphite-phase C afterwards3N4/ calcite nanosheet composite material；
D is absorption Cd2+Ultra-thin graphite-phase C afterwards3N4After the aggregated chlorination aluminum flocculation coagulation of/calcite nanosheet composite material).
Fig. 2 be embodiment 2 in Related product scanning electron microscope (SEM) photograph (in figure, a be ultra-thin graphite-phase C3N4/ calcite nanometer sheet
Composite material；B is absorption Cd2+Ultra-thin graphite-phase C afterwards3N4The aggregated chlorination aluminum flocculation of/calcite nanosheet composite material is poly-
After heavy).
Specific embodiment
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of ultra-thin graphite-phase C3N4/ calcite nanosheet composite material, with ultra-thin graphite-phase C3N4For carrier, and it is super
Thin graphite-phase C3N4Supported on carriers is modified with calcite nanometer sheet.Wherein, ultra-thin graphite-phase C3N4For two-dimensional layer nanometer sheet knot
Structure (2D structure), calcite nanometer sheet are 3D structure, and the load capacity of calcite nanometer sheet is the 29% of carrier quality.
Above-mentioned ultra-thin graphite-phase C3N4The preparation method of/calcite nanosheet composite material, comprising the following steps:
(1) blocky graphite phase C3N4Preparation: 80g melamine is put into crucible, with 2 DEG C/min's in Muffle furnace
Heating rate is warming up to 500 DEG C, keeps constant temperature 2h, is then down to room temperature with identical rate of temperature fall, obtains pale yellow powder i.e.
For blocky graphite phase C3N4；
(2) ultra-thin graphite-phase C3N4The preparation of nanometer sheet: the blocky graphite phase C that step (1) is prepared3N4Powder
0.2g is dispersed in 200mL deionized water, is ultrasonically treated 15h through 40KHz, is then allowed to stand 30min, is filtered to remove and remaining is not taken off
The C fallen3N4Nano particle and big block-like nanometer sheet, gained suspension is ultra-thin graphite-phase C3N4Nanometer sheet suspension；
(3) ultra-thin graphite-phase C3N4The preparation of/calcite nanosheet composite material: by 50g 0.1M Ca2+Solution and 50g
Ultra-thin graphite-phase C3N4The mixing of nanometer sheet suspension, is ultrasonically treated 2h through 40KHz；Sonicated Ca will be housed2+Solution with
Ultra-thin C3N4The beaker of nanometer sheet mixed solution be equipped with (NH4)2CO3Solid ((NH4)2CO3By guarantee, it is waved the dosage of solid
The CO of sending2Amount be calcite needed for CO23 times of dosage) surface plate be put into closed drier bottom together, with sealing
Film seals surface plate, and 5 pinhead-sized holes are being made on sealed membrane, in order to CO2It spreads, reacts 15h at 35 DEG C,
Then at 4000r/min, it is centrifuged 5min, is centrifuged 3 times, it is ultra-thin graphite-phase C that resulting precipitating, which is spontaneously dried,3N4/ side solution
Stone nanosheet composite material.
The ultra-thin graphite-phase C that the present embodiment is prepared3N4/ calcite nanosheet composite material is applied to Cadmium In The Water Body
The solidification of ion, specifically includes the following steps:
(1) ultra-thin graphite-phase C is weighed3N4It is respectively 1mg/ that/calcite nanosheet composite material 0.1g, which is placed in 200mL concentration,
L、5mg/L、10mg/L、15mg/L Cd2+In solution, setting constant temperature oscillator temperature is 25 DEG C, shakes rate in 180-200r/
Min, concussion reaction 3-6h；Measure the Cd after absorption respectively with ICP-MS2+Concentration calculates Cd2+Go adsorption rate, result is such as
Shown in table 1；
(2) 0.2g aluminium polychloride is added in each solution obtained by step (1), through 40KHz ultrasound 16h, 2h is stood, through super
Thin graphite-phase C3N4The Cd of/calcite nanosheet composite material absorption2+Carry out polymeric precipitation；
(3) flocculent deposit obtained by step (2) be centrifuged 5min in the case where centrifugation rate is 4000r/min, be centrifuged 3 times,
Remove Cd in water body2+。
Embodiment 2:
A kind of ultra-thin graphite-phase C3N4/ calcite nanosheet composite material, with ultra-thin graphite-phase C3N4For carrier, and it is super
Thin graphite-phase C3N4Supported on carriers is modified with calcite nanometer sheet.Wherein, ultra-thin graphite-phase C3N4For two-dimensional layer nanometer sheet knot
Structure (2D structure), calcite nanometer sheet are 3D structure, and the load capacity of calcite nanometer sheet is the 37% of carrier quality.
Above-mentioned ultra-thin graphite-phase C3N4The preparation method of/calcite nanosheet composite material, comprising the following steps:
(1) blocky graphite phase C3N4Preparation: 90g melamine is put into crucible, with 4 DEG C/min's in Muffle furnace
Heating rate is warming up to 600 DEG C, keeps constant temperature 3h, is then down to room temperature with identical rate of temperature fall, obtains pale yellow powder i.e.
For blocky graphite phase C3N4；
(2) ultra-thin graphite-phase C3N4The preparation of nanometer sheet: the blocky graphite phase C that step (1) is prepared3N4Powder
0.4g is dispersed in 400mL deionized water, is ultrasonically treated 18h through 40KHz, is then allowed to stand 40min, is filtered to remove and remaining is not taken off
The C fallen3N4Nano particle and big block-like nanometer sheet, gained suspension is ultra-thin graphite-phase C3N4Nanometer sheet suspension；
(3) ultra-thin graphite-phase C3N4The preparation of/calcite nanosheet composite material: by 30g 0.1M Ca2+Solution and 70g
Ultra-thin graphite-phase C3N4The mixing of nanometer sheet suspension, is ultrasonically treated 1h through 40KHz；Sonicated Ca will be housed2+Solution with
Ultra-thin C3N4The beaker of nanometer sheet mixed solution be equipped with (NH4)2CO3Solid ((NH4)2CO3By guarantee, it is waved the dosage of solid
The CO of sending2Amount be calcite needed for CO23 times of dosage) surface plate be put into closed drier bottom together, with sealing
Film seals surface plate, and 3 pinhead-sized holes are being made on sealed membrane, in order to CO2It spreads, reacts 15h at 30 DEG C,
Then at 4000r/min, it is centrifuged 5min, is centrifuged 3 times, it is ultra-thin graphite-phase C that resulting precipitating, which is spontaneously dried,3N4/ side solution
Stone nanosheet composite material.
Fig. 1 is the ultra-thin graphite-phase C that the present embodiment is prepared3N4The transmission electron microscope table of/calcite nanosheet composite material
Sign figure.Show graphite-phase C in Fig. 1 a3N4Successfully it has been prepared into graphite-phase graphite-phase C3N4Two-dimensional nano thin slice；Fig. 1 b is said
The calcite that diamond shape is illustrated successfully is loaded to graphite-phase C3N4On two-dimensional nano thin slice；Fig. 1 c demonstrate calcite at
Function suction appends Cd element；Fig. 1 d show absorption after Cd calcite by polyaluminium aluminum flocculation coagulation so that Cd is first
Element solidification.
Fig. 2 is the ultra-thin graphite-phase C that the present embodiment is prepared3N4The scanning electron microscope table of/calcite nanosheet composite material
Sign figure.Fig. 2 a indicates that the calcite with 3D structure has successfully loaded to two-dimensional graphite-phase C3N4In nanometer sheet.Attached drawing 2b
Show the calcite for adsorbing Cd by polyaluminium aluminum flocculation coagulation, so that Cd element solidifies.
The ultra-thin graphite-phase C that the present embodiment is prepared3N4/ calcite nanosheet composite material is applied to Cadmium In The Water Body
The solidification of ion, specifically includes the following steps:
(1) ultra-thin graphite-phase C is weighed3N4It is respectively 1mg/ that/calcite nanosheet composite material 0.1g, which is placed in 200mL concentration,
L、5mg/L、10mg/L、15mg/L Cd2+In solution, setting constant temperature oscillator temperature is 25 DEG C, shakes rate in 180-200r/
Min, concussion reaction 3-6h；Measure the Cd after absorption respectively with ICP-MS2+Concentration calculates Cd2+Go adsorption rate, result is such as
Shown in table 1；
(2) 0.2g aluminium polychloride is added in each solution obtained by step (1), through 40KHz ultrasound 16h, 2h is stood, through super
Thin graphite-phase C3N4The Cd of/calcite nanosheet composite material absorption2+Carry out polymeric precipitation；
(3) flocculent deposit obtained by step (2) be centrifuged 5min in the case where centrifugation rate is 4000r/min, be centrifuged 3 times,
Remove Cd in water body2+。
Embodiment 3:
A kind of ultra-thin graphite-phase C3N4/ calcite nanosheet composite material, with ultra-thin graphite-phase C3N4For carrier, and it is super
Thin graphite-phase C3N4Supported on carriers is modified with calcite nanometer sheet.Wherein, ultra-thin graphite-phase C3N4For two-dimensional layer nanometer sheet knot
Structure (2D structure), calcite nanometer sheet are 3D structure, and the load capacity of calcite nanometer sheet is the 22% of carrier quality.
Above-mentioned ultra-thin graphite-phase C3N4The preparation method of/calcite nanosheet composite material, comprising the following steps:
(1) blocky graphite phase C3N4Preparation: 100g melamine is put into crucible, with 6 DEG C/min's in Muffle furnace
Heating rate is warming up to 650 DEG C, keeps constant temperature 4h, is then down to room temperature with identical rate of temperature fall, obtains pale yellow powder i.e.
For blocky graphite phase C3N4；
(2) ultra-thin graphite-phase C3N4The preparation of nanometer sheet: the blocky graphite phase C that step (1) is prepared3N4Powder
0.5g is dispersed in 500mL deionized water, is ultrasonically treated 20h through 40KHz, is then allowed to stand 45min, is filtered to remove and remaining is not taken off
The C fallen3N4Nano particle and big block-like nanometer sheet, gained suspension is ultra-thin graphite-phase C3N4Nanometer sheet suspension；
(3) ultra-thin graphite-phase C3N4The preparation of/calcite nanosheet composite material: by 40g 0.1M Ca2+Solution and 60g
Ultra-thin graphite-phase C3N4The mixing of nanometer sheet suspension, is ultrasonically treated 1.5h through 40KHz；Sonicated Ca will be housed2+Solution
With ultra-thin C3N4The beaker of nanometer sheet mixed solution be equipped with (NH4)2CO3Solid ((NH4)2CO3The dosage of solid is its institute of guarantee
The CO volatilized2Amount be calcite needed for CO23 times of dosage) surface plate be put into closed drier bottom together, with envelope
Membrana oralis seals surface plate, and 4 pinhead-sized holes are being made on sealed membrane, in order to CO2It spreads, is reacted at 35 DEG C
15h is centrifuged 5min then at 4000r/min, is centrifuged 3 times, and it is ultra-thin graphite-phase C that resulting precipitating, which is spontaneously dried,3N4/
Calcite nanosheet composite material.
The ultra-thin graphite-phase C that the present embodiment is prepared3N4/ calcite nanosheet composite material is applied to Cadmium In The Water Body
The solidification of ion, specifically includes the following steps:
(1) ultra-thin graphite-phase C is weighed3N4It is respectively 1mg/ that/calcite nanosheet composite material 0.1g, which is placed in 200mL concentration,
L、5mg/L、10mg/L、15mg/L Cd2+In solution, setting constant temperature oscillator temperature is 25 DEG C, shakes rate in 180-200r/
Min, concussion reaction 3-6h；Measure the Cd after absorption respectively with ICP-MS2+Concentration calculates Cd2+Go adsorption rate, result is such as
Shown in table 1；
(2) 0.2g aluminium polychloride is added in each solution obtained by step (1), through 40KHz ultrasound 16h, 2h is stood, through super
Thin graphite-phase C3N4The Cd of/calcite nanosheet composite material absorption2+Carry out polymeric precipitation；
(3) flocculent deposit obtained by step (2) be centrifuged 5min in the case where centrifugation rate is 4000r/min, be centrifuged 3 times,
Remove Cd in water body2+。
Comparative example 1:
Calcite is directly used for the solidification of Cadmium In The Water Body ion, specific steps are as follows: calcite 0.1g is set in this comparative example
In 200mL concentration be respectively 1mg/L, 5mg/L, 10mg/L, 15mg/LCd2+In solution, setting constant temperature oscillator temperature is 25 DEG C,
Rate is shaken in 180-200r/min, concussion reaction 3-6h；Measure the Cd after absorption respectively with ICP-MS2+Concentration calculates Cd2+
Adsorption efficiency, the results are shown in Table 1.
Table 1: various concentration Cd is adsorbed in embodiment 1-3 and comparative example 12+Adsorption experiment data
As shown in Table 1, ultra-thin graphite-phase C made from the preparation method that embodiment 1, embodiment 2 and embodiment 3 use3N4/
Calcite nanosheet composite material, for the calcite of comparative example 1, for Cd2+Adsorption efficiency be remarkably reinforced, this
It is since the surface of calcite is smooth and crystallinity is high, without boundary defect, so that calcite is to Cd2+Adsorption capacity it is smaller.
Claims (10)
1. a kind of ultra-thin graphite-phase C3N4/ calcite nanosheet composite material, which is characterized in that the composite material is with ultra-thin stone
Black phase C3N4For carrier, the ultra-thin graphite-phase C3N4Supported on carriers has calcite nanometer sheet.
2. ultra-thin graphite-phase C according to claim 13N4/ calcite nanosheet composite material, which is characterized in that described super
Thin graphite-phase C3N4On carrier, the load capacity of calcite nanometer sheet is the 20-40% of carrier quality.
3. ultra-thin graphite-phase C according to claim 1 or 23N4/ calcite nanosheet composite material, which is characterized in that institute
State ultra-thin graphite-phase C3N4For two-dimensional layer nanometer chip architecture, the calcite nanometer sheet is 3D structure.
4. a kind of ultra-thin graphite-phase C3N4The preparation method of/calcite nanosheet composite material, which is characterized in that including following step
It is rapid:
(1) ultra-thin graphite-phase C is prepared3N4Carrier suspension；
(2) by Ca2+Ultra-thin graphite-phase C obtained in solution and step (1)3N4Carrier suspension ultrasonic mixing is uniform, then passes to
CO2Reaction, centrifugal treating after fully reacting collect precipitating, obtain ultra-thin graphite-phase C after dry3N4/ calcite nanometer sheet is multiple
Condensation material.
5. the preparation method according to claim 4, which is characterized in that prepare ultra-thin graphite-phase C3N4Carrier suspension includes
Following steps: melamine is put into crucible, heats to obtain blocky graphite phase C in Muffle furnace3N4；Blocky graphite is taken again
Phase C3N4It is scattered in deionized water, through ultrasound, stewing process, is filtered to remove undispersed blocky graphite phase C3N4, gained filtrate
As ultra-thin graphite-phase C3N4Carrier suspension；Wherein, the blocky graphite phase C3N4Weight ratio with deionized water is 0.1:
100。
6. the preparation method according to claim 4, which is characterized in that the Ca2+Solution and ultra-thin graphite-phase C3N4Carrier is outstanding
The weight ratio of supernatant liquid is (30-50): (50-70), the Ca2+Ca in solution2+Concentration is 0.1M.
7. the preparation method according to claim 4, which is characterized in that in the step (2), when ultrasonic treatment, at ultrasound
Reason frequency is 30-50KHz, sonication treatment time 1-2h；When centrifugal treating, centrifugation rate 4000-5000r/min, centrifugation
Time is 5-15min, and centrifugation number is 3-5 times.
8. preparation method according to claim 5, which is characterized in that in Muffle furnace heat treatment, with 2-6 DEG C/min's
Heating rate is warming up to 500-650 DEG C, keeps stationary temperature 2-4h, is then down to room temperature with identical 2-6 DEG C/min rate of temperature fall；
When ultrasound, stewing process, ultrasonic treatment frequency is 30-50KHz, sonication treatment time 15-20h, time of repose 30-
45min。
9. preparation method according to claim 4, which is characterized in that in the step (2), be passed through CO2The time of reaction
For 12-20h；It is passed through CO2The mode of reaction is as follows: at 30-35 DEG C, by sonicated obtained mixed solution and being equipped with
(NH4)2CO3The surface plate of solid is put into together in closed drier, and is sealed surface plate with sealed membrane, and in sealed membrane
Upper aperture；Wherein, (NH4)2CO3The dosage of the solid CO that it is volatilized by guarantee2Amount be calcite needed for CO2The 2- of dosage
5 times.
10. a kind of preparation method as claimed in any one of claims 1-3 or as described in any one of claim 4-9 obtains
The ultra-thin graphite-phase C arrived3N4The application of/calcite nanosheet composite material, which is characterized in that be used for the composite material solid
Change the Cd in water body2+；Solidification process is the following steps are included: by the composite material and containing Cd2+Waste liquid is uniformly mixed, reaction one
Aluminium polychloride progress coagulation is added after the section time to handle to obtain flocculent deposit, centrifugation removal flocculent deposit is i.e. completely at Cd2+Gu
Change process；Wherein, contain Cd when described2+Cd in waste liquid2+When concentration is 1-15mg/L, the additive amount of the composite material is 0.2-
2.5g/L。
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