CN109833847A - A kind of nitride porous boron adsorbent and preparation method thereof that nickel oxide is modified - Google Patents
A kind of nitride porous boron adsorbent and preparation method thereof that nickel oxide is modified Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 48
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 43
- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 39
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052582 BN Inorganic materials 0.000 claims abstract description 46
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 230000003115 biocidal effect Effects 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 7
- 231100000719 pollutant Toxicity 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 244000144992 flock Species 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 238000005119 centrifugation Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- 239000004098 Tetracycline Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 229960002180 tetracycline Drugs 0.000 description 7
- 229930101283 tetracycline Natural products 0.000 description 7
- 235000019364 tetracycline Nutrition 0.000 description 7
- 150000003522 tetracyclines Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000008236 heating water Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000003403 water pollutant Substances 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- -1 nickel peroxide Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention is a kind of modified nitride porous boron adsorbent and preparation method thereof of nickel oxide, the following steps are included: porous boron nitride is dispersed in formation porous boron nitride dispersion liquid in pure water, the mass ratio of porous boron nitride and pure water is 1:200~600 in porous boron nitride dispersion liquid；According to six water nickel nitrates and quality of pure water ratio 1:50~100, six water nickel nitrates are dissolved in pure water and are added dropwise in porous boron nitride dispersion liquid, the molar ratio of porous boron nitride and six water nickel nitrates is 1:0.005~0.1, stirring 6~for 24 hours, still aging 6~for 24 hours, by obtained 8000~11000rpm of mixed solution centrifugation, pure water washing 3 times it is above, be freeze-dried after, 300~500 DEG C of 0.5~3h of processing in Muffle furnace are placed in, the modified nitride porous boron adsorbent of nickel oxide is obtained.The adsorbent not only has high specific surface area and pore volume, but also has a great deal of surface-active site and functional group, can effectively remove antibiotic pollutant in water.
Description
Technical field
The present invention relates to the modified nitride porous boron adsorbent of adsorbent material field more particularly to a kind of nickel oxide and its
Preparation method.
Background technique
Adsorption technology with its low energy consumption, easy to operate, without secondary pollution the advantages that in the pollution control side of water body and gas
Face receives the extensive concern of people, and efficient designing and preparing for adsorbent is a most important side in adsorption technology
Face.Currently, the conventional adsorbents material such as common adsorbent, including active carbon, montmorillonite, zeolite, absorption resin, due to mesh
Mark pollutant affinity is poor, the disadvantages of adsorption capacity is low and cyclic utilization rate is not high limits it in actual production and life
Using.Therefore, finding and prepare with high-adsorption-capacity, excellent stability and renewable high-efficiency adsorbent is to be badly in need of
The problem of solution.
Porous hexagonal boron nitride (h-BN) is the analog of graphite, have specific surface area is high, cellular structure is abundant, chemistry and
Hot property stabilization and hydrophobic characteristic have very big application latent in the fields such as hydrogen storage, gas absorption and separation, water body purification
Power.Usual situation, purity, specific surface area, pore-size distribution, surface defect and the number of functional groups of nitride porous boron material are to influence
An important factor for it is to water pollutant affinity and adsorption capacity, so it is further for being modified activation to porous boron nitride
The method for improving its absorption property.The method having been reported that at present is added using P123 or hexamethylenetetramine as surfactant
Enter into boric acid and melamine solution to prepare boron nitride presoma, then reheating solution forms the active boron nitride of high-specific surface area
Fiber, but the surfactant added can be decomposed into H in Pintsch process2O、CO2And NH3Etc. gas molecules evolution, only increase
Added adsorbent specific surface area and pore volume and do not increase surface-active site and functional group, therefore such methods have
Certain limitation.Develop that a kind of novel effective surface there are a large amount of active sites and the porous boron nitride of functional group is to improve it
To the important channel of water pollutant affinity and adsorption capacity.
Summary of the invention
Be directed to the defect of the prior art, the present invention provide a kind of nitride porous boron adsorbent that nickel oxide is modified and its
Preparation method, adsorbent specific surface area and pore volume are concerned only with when solving existing modified active boron nitride to be influenced and ignores
The problem of surface-active site and number of functional groups influence is developed a kind of surface for effectively removing antibiotic pollutant in water and is changed
Property nitridation boron adsorbent.
The technical scheme adopted by the invention is that:
A kind of nitride porous boron adsorbent and preparation method thereof that nickel oxide is modified, comprising the following steps:
Porous boron nitride is dispersed in pure water and forms porous boron nitride dispersion liquid, it is porous in porous boron nitride dispersion liquid
The mass ratio of boron nitride and pure water is 1:200~600；According to six water nickel nitrates and quality of pure water ratio 1:50~100, by six
Water nickel nitrate is dissolved in pure water and is added dropwise in porous boron nitride dispersion liquid, porous boron nitride and six water nickel nitrates
Molar ratio is 1:0.005~0.1, stirring 6~for 24 hours, and still aging 6~for 24 hours, the 8000~11000rpm of mixed solution that will be obtained
Centrifugation, pure water washing 3 times it is above, be freeze-dried after, be placed in 300~500 DEG C of 0.5~3h of processing in Muffle furnace, obtain nickel oxygen
The modified nitride porous boron adsorbent of compound.
The preparation process of the porous boron nitride is:
Step 1: boric acid and melamine that molar ratio is 1.8:1~3:1 are added in the container for filling pure water,
Heating water bath is to 80~95 DEG C again, stirs to clear transparent solutions are obtained, and wherein the concentration of boric acid is 0.2~0.4mol/L, and three
The concentration of poly cyanamid is 0.1~0.2mol/L, by obtained clear transparent solutions in 60~80 DEG C of 2~12h of heat preservation, then is dropped naturally
To room temperature, white flock precipitate is obtained, suction filtration obtains white solid, then the drying 12~for 24 hours at 70~80 DEG C, obtains white fibre
Tie up shape presoma；
Step 2: by under nitrogen atmosphere of the presoma obtained in step 1 in 100~200mL/min, 900~1200
DEG C calcining 2~4h, obtain porous boron nitride.
Compared with prior art, the beneficial effects of the invention are that:
(1) the method for the present invention is using boron nitride as substrate, and loads nickel oxide on it under suitable technique, obtained nickel
Oxide modifying porous boron nitride is threadiness, about 50~100 μm of length, about 0.5~3 μm of diameter, has biggish draw ratio
With complete uniform fibrous structure；The specific surface area of the modified porous nitridation boron adsorbent of nickel oxide can reach 583.723m2/
G, total pore volume are up to 0.373cm3/ g makes it have higher adsorption capacity.
(2) the modified porous nitridation boron adsorbent of nickel oxide that the present invention obtains is up to the removal rate of tetracycline in water
99.182%, adsorption capacity is up to 440.069mg/g.
(3) there are many nickel nanometers for the modified porous boron nitride adsorbent surface load of the nickel oxide that the method for the present invention obtains
Grain, the porous boron nitride that can be used as activated adoption position and high-specific surface area generate synergistic effect, increase the absorption parent to antibiotic
With power and adsorption capacity, the application using nitride porous boron fibre as adsorbent processing water in antibiotic pollutant, be added nickel it
The adsorbance and removal rate of original boron nitride can be significantly improved afterwards.
(4) raw material that uses of the present invention is boric acid, melamine and Nickelous nitrate hexahydrate, cheap, preparation method is simple
It is single, it can be realized large-scale production, can be used in actual production life.The method is due to boron nitride and the equal energy of Nickelous nitrate hexahydrate
Be dispersed in water well, compared to traditional infusion process can make load metal is more uniform, nickel oxide particle is smaller, golden
Category usage amount is less, and obtained modified adsorbent activated adoption position is more, bigger to the adsorbance of antibiotic.
Detailed description of the invention
Attached drawing 1 is the XRD diagram of the modified porous nitridation boron adsorbent of the nickel oxide in example 1.
Attached drawing 2 is the FT-IR figure of the modified porous nitridation boron adsorbent of the nickel oxide in example 1.
Attached drawing 3 is the SEM figure of the modified porous nitridation boron adsorbent of the nickel oxide in example 1.
Attached drawing 4 is the TEM figure of the modified porous nitridation boron adsorbent of the nickel oxide in example 1.
Attached drawing 5 is nitrogen adsorption-desorption isotherm of the modified porous nitridation boron adsorbent of the nickel oxide in example 1.
Attached drawing 6 is the graph of pore diameter distribution of the modified porous nitridation boron adsorbent of the nickel oxide in example 1.
Attached drawing 7 is the modified porous nitridation boron adsorbent of nickel oxide and unmodified porous nitrogen in example 1 and embodiment 4-7
Change boron to the comparison diagram of tetracycline removal rate.
Specific embodiment
Further detailed description is done to the present invention below with reference to embodiment and attached drawing, it should be noted that following examples
Only the present invention is explained, embodiments of the present invention cannot be limited.
The preparation method of the modified nitride porous boron adsorbent of nickel oxide of the present invention, comprising the following steps:
Step 1: by molar ratio be 1.8:1~3:1 boric acid and melamine be added to fill pure water (deionized water,
Distilled water all can) container in, then heating water bath is to 80~95 DEG C, stirs to clear transparent solutions are obtained, wherein boric acid is dense
Degree is 0.2~0.4mol/L, and the concentration of melamine is 0.1~0.2mol/L, by obtained clear transparent solutions 60~80
DEG C 2~12h of heat preservation, then is down to room temperature naturally, obtains white flock precipitate, filter and obtain white solid, then at 70~80 DEG C
Drying 12~for 24 hours, obtain white fibrous presoma；
Step 2: by under nitrogen atmosphere of the presoma obtained in step 1 in 100~200mL/min, 900~1200
DEG C calcining 2~4h, obtain porous boron nitride；
Step 3: porous boron nitride obtained in step 2 is dispersed in the pure water of 200~600 times of its quality, six
Water nickel nitrate is dissolved in the pure water of 50~100 times of its quality and is added dropwise in porous boron nitride dispersion liquid, porous nitrogen
The molar ratio for changing boron and six water nickel nitrates is 1:0.005~0.1, stirring 6~for 24 hours, still aging 6~for 24 hours, the mixing that will be obtained
8000~11000rpm of solution be centrifuged 3~10min, pure water washing 3 times it is above, be freeze-dried after, be placed in 300 in Muffle furnace~
500 DEG C of 0.5~3h of processing obtain the modified nitride porous boron adsorbent of nickel oxide.
The method of the present invention is synthesized using three-step approach: the first step, according to a certain percentage by the compound containing boron source and nitrogen source
It is mixed to form presoma；Synthesized presoma is calcined under inert gas protection, obtains high-specific surface area by second step
Nitride porous boron fibre；Nickel oxide is equably loaded to nitride porous boron surface, increases Adsorption by third step
Point enhances the affinity to antibiotic molecule, improves adsorption capacity and removal rate to antibiotic pollutant.The adsorbent
It applies in going water removal in terms of antibiotic pollutant.
In step 3 of the present invention when dispersing boron nitride, corresponding amount of purified water should be enough, can sufficiently divide
Dissipate, six water nickel nitrates are added dropwise in boron nitride dispersion again after being dissolved completely in pure water, guarantee enough centrifugal rotational speeds and
Time obtains the modified nitride porous boron adsorbent of nickel oxide.
Embodiment 1
The present embodiment prepares the modified nitride porous boron adsorbent of nickel oxide:
Step 1: boric acid and melamine that molar ratio is 2:1 are added in the container for filling deionized water, water-bath adds
Heat is stirred to 95 DEG C to clear transparent solutions are obtained, and wherein the concentration of boric acid is 0.4mol/L, and the concentration of melamine is
0.2mol/L by obtained clear solution in 80 DEG C of heat preservation 2h, then is down to room temperature naturally, obtains white flock precipitate, filter
12h is dried to white solid, then at 70 DEG C, obtains white fibrous presoma；
Step 2: by under nitrogen atmosphere of the presoma obtained in step 1 in 100mL/min, 900 DEG C of calcining 4h are obtained
To porous boron nitride；
Step 3: taking 0.5g to be dispersed in the deionized water of 400 times of its quality porous boron nitride obtained in step 2,
Six water nickel nitrates are dissolved in the pure water of 50 times of its quality and are added dropwise in porous boron nitride dispersion liquid, porous boron nitride
Be 1:0.025 with the molar ratios of six water nickel nitrates, stirring for 24 hours, it is still aging for 24 hours, by obtained mixed solution 10000rpm from
After heart 5min, pure water washing 3 times, freeze-drying, 500 DEG C of processing 3h in Muffle furnace are placed in, obtain the more of nickel oxide modification
Hole nitrogenizes boron adsorbent.
Fig. 1 is the XRD diagram of the modified porous nitridation boron adsorbent of nickel oxide obtained in embodiment 1, therefrom can be bright
Aobvious finds out that the diffraction maximum for belonging to hexagonal boron nitride, explanation can be successfully prepared porous hexagonal boron nitride, in addition to this may be used also
To see the diffraction maximum for belonging to nickel peroxide, illustrate that nickel oxide has successfully loaded to the surface of porous boron nitride, and nickel is
Crystalline state can provide more active sites；
Fig. 2 is the FT-IR figure of the modified porous nitridation boron adsorbent of nickel oxide obtained in embodiment 1, surface band
There are the functional groups such as hydroxyl, can be used as activated adoption site and be beneficial to the progress adsorbed.
Fig. 3 is the SEM figure of the modified porous nitridation boron adsorbent of nickel oxide obtained in embodiment 1, porous boron nitride
In threadiness, there is biggish draw ratio, size is more uniform, its is rough after nickel-loaded, it can be seen that equally distributed
Little particle.
Fig. 4 is the TEM figure of the modified porous nitridation boron adsorbent of nickel oxide obtained in embodiment 1, therefrom can be more
Significantly see the nickel particle of porous boron nitride area load, the presence of these nickel particles can effectively improve porous boron nitride
Its removal rate to tetracycline is improved in turn to the absorption affinity of tetracycline；Along with the specific surface area of this adsorbent is up to
583.723m2/ g, total pore volume are up to 0.373cm3/ g (the obtained modified porous nitridation of nickel oxide in such as Fig. 5 embodiment 1
The modified porous boron nitride absorption of obtained nickel oxide in the nitrogen adsorption desorption isotherm and Fig. 6 embodiment 1 of boron adsorbent
Shown in the graph of pore diameter distribution of agent), the nickel oxide active site collective effect of high-specific surface area and surface modification makes nickel obtained
Oxide modifying nitride porous boron adsorbent is increased to the adsorption capacity of tetracycline from unmodified 64.573%
99.182% (such as modified porous nitridation boron adsorbent of Fig. 7 difference nickel oxide amount and unmodified porous boron nitride move tetracycline
Shown in comparison diagram except rate).
Embodiment 2
Step 1: boric acid and melamine that molar ratio is 2:1 are added in the container for filling pure water, heating water bath
It to 80 DEG C, stirs to clear transparent solutions are obtained, wherein the concentration of boric acid is 0.2mol/L, and the concentration of melamine is
0.1mol/L by obtained clear solution in 60 DEG C of heat preservation 12h, then is down to room temperature naturally, obtains white flock precipitate, filter
It is dried for 24 hours to white solid, then at 80 DEG C, obtains white fibrous presoma；
Step 2: by under nitrogen atmosphere of the presoma obtained in step 1 in 200mL/min, 1100 DEG C of calcining 2h,
Obtain porous boron nitride；
Step 3: taking 0.5g to be dispersed in the pure water of 400 times of its quality porous boron nitride obtained in step 2, and six
Water nickel nitrate is dissolved in the pure water of 50 times of its quality and is added dropwise in porous boron nitride dispersion liquid, porous boron nitride and
The molar ratio of six water nickel nitrates is 1:0.025, stirs 6h, still aging 6h, and obtained mixed solution 10000rpm is centrifuged
After 5min, pure water washing 3 times, freeze-drying, 300 DEG C of processing 0.5h in Muffle furnace are placed in, obtain the more of nickel oxide modification
Hole nitrogenizes boron adsorbent.
Embodiment 3
Step 1: boric acid and melamine that molar ratio is 2:1 are added in the container for filling pure water, heating water bath
It to 90 DEG C, stirs to clear transparent solutions are obtained, wherein the concentration of boric acid is 0.3mol/L, and the concentration of melamine is
0.15mol/L by obtained clear solution in 70 DEG C of heat preservation 6h, then is down to room temperature naturally, obtains white flock precipitate, filter
12h is dried to white solid, then at 70 DEG C, obtains white fibrous presoma；
Step 2: by under nitrogen atmosphere of the presoma obtained in step 1 in 100mL/min, 1000 DEG C of calcining 3h,
Obtain porous boron nitride；
Step 3: taking 0.5g to be dispersed in the pure water of 400 times of its quality porous boron nitride obtained in step 2, and six
Water nickel nitrate is dissolved in the pure water of 50 times of its quality and is added dropwise in porous boron nitride dispersion liquid, porous boron nitride and
The molar ratio of six water nickel nitrates is 1:0.025, stirs 12h, still aging 12h, and obtained mixed solution 10000rpm is centrifuged
After 5min, pure water washing 3 times, freeze-drying, 400 DEG C of processing 2h in Muffle furnace are placed in, obtain the porous of nickel oxide modification
Nitrogenize boron adsorbent.
Embodiment 4,5,6,7
The molar ratio of porous boron nitride and six water nickel nitrates in 1 step 3 of embodiment is changed to 1:0.005 respectively, 1:
0.0125,1:0.05 and 1:0.1, other operations obtain that product is similar to Example 1 with embodiment 1, to tetracycline
Removal rate is shown in Fig. 7.The molar ratio of the two can show absorption property well within the scope of the application, preferred proportion 1:
0.025-0.05。
The present invention does not address place and is suitable for the prior art.
Claims (4)
1. a kind of modified nitride porous boron adsorbent and preparation method thereof of nickel oxide, comprising the following steps:
Porous boron nitride is dispersed in formation porous boron nitride dispersion liquid in pure water, nitride porous in porous boron nitride dispersion liquid
The mass ratio of boron and pure water is 1:200~600；According to six water nickel nitrates and quality of pure water ratio 1:50~100, by six water nitre
Sour nickel is dissolved in pure water and is added dropwise in porous boron nitride dispersion liquid, mole of porous boron nitride and six water nickel nitrates
Than for 1:0.005~0.1, stirring 6~for 24 hours, still aging 6~for 24 hours, by obtained 8000~11000rpm of mixed solution from
The heart, pure water washing 3 times or more, after freeze-drying, be placed in 300~500 DEG C of 0.5~3h of processing in Muffle furnace, obtain nickel and aoxidize
The modified nitride porous boron adsorbent of object.
2. preparation method according to claim 1, which is characterized in that the preparation process of the porous boron nitride is:
Step 1: boric acid and melamine that molar ratio is 1.8:1~3:1 are added in the container for filling pure water, then water
Bath is heated to 80~95 DEG C, stirs to clear transparent solutions are obtained, and wherein the concentration of boric acid is 0.2~0.4mol/L, melamine
The concentration of amine is 0.1~0.2mol/L, by obtained clear transparent solutions in 60~80 DEG C of 2~12h of heat preservation, then is down to room naturally
Temperature, obtains white flock precipitate, and suction filtration obtains white solid, then the drying 12~for 24 hours at 70~80 DEG C, obtains white fibrous
Presoma；
Step 2: by under nitrogen atmosphere of the presoma obtained in step 1 in 100~200mL/min, 900~1200 DEG C are forged
2~4h is burnt, porous boron nitride is obtained.
3. preparation method according to claim 1, which is characterized in that the molar ratio of porous boron nitride and six water nickel nitrates is
1:0.025~0.05.
4. the modified nitride porous boron adsorbent of any nickel oxide of claim 1-3, which, which applies, is being removed
In water in terms of antibiotic pollutant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910264490.9A CN109833847B (en) | 2019-04-03 | 2019-04-03 | Nickel oxide modified porous boron nitride adsorbent and preparation method thereof |
Applications Claiming Priority (1)
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| CN112808294A (en) * | 2021-01-05 | 2021-05-18 | 中国石油大学(华东) | Boron nitride/nickel oxide composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110586022A (en) * | 2019-09-18 | 2019-12-20 | 沈阳航空航天大学 | Method for removing fatty acid from textile industrial wastewater by using acid-base modified porous boron nitride |
| CN110668407A (en) * | 2019-10-18 | 2020-01-10 | 福州大学 | Preparation method of rod-shaped hexagonal boron nitride foam and application of rod-shaped hexagonal boron nitride foam in oxidative dehydrogenation of propane |
| CN110668407B (en) * | 2019-10-18 | 2022-10-11 | 福州大学 | Preparation method of rod-shaped hexagonal boron nitride foam and application of rod-shaped hexagonal boron nitride foam in oxidative dehydrogenation of propane |
| CN112808294A (en) * | 2021-01-05 | 2021-05-18 | 中国石油大学(华东) | Boron nitride/nickel oxide composite material and preparation method and application thereof |
| CN112808294B (en) * | 2021-01-05 | 2023-02-17 | 中国石油大学(华东) | Boron nitride/nickel oxide composite material and preparation method and application thereof |
| CN116116374A (en) * | 2023-03-09 | 2023-05-16 | 河北工业大学 | La (La) 2 O 3 Preparation method and application of BNNFs composite adsorbent |
| CN116116374B (en) * | 2023-03-09 | 2024-05-17 | 河北工业大学 | La (La)2O3Preparation method and application of BNNFs composite adsorbent |
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