CN110433844A - One kind containing Cr for efficient process6+(B, O) the codope g-C of waste water3N4The preparation method of photochemical catalyst - Google Patents
One kind containing Cr for efficient process6+(B, O) the codope g-C of waste water3N4The preparation method of photochemical catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002699 waste material Substances 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000004202 carbamide Substances 0.000 claims abstract description 31
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 28
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 30
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- DXOMQVWFKDKKQV-UHFFFAOYSA-N C(CO)O.[N+](=O)([O-])[O-].[Bi+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound C(CO)O.[N+](=O)([O-])[O-].[Bi+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] DXOMQVWFKDKKQV-UHFFFAOYSA-N 0.000 description 1
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- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses one kind to contain Cr for efficient process6+(B, O) the codope g-C of waste water3N4The preparation method of photochemical catalyst, the preparation method weigh urea 8-12g, NaBH the following steps are included: step 140.1g-0.8g, and by urea and NaBH4It is put into mortar, grinding 10-30min makes two components be uniformly mixed to obtain mixture A；Step 2, mixture A is put into crucible, and closed the lid, be placed in Muffle furnace and calcine 1-3 hours, after furnace cooled to room temperature, take out semi-finished product；Step 3, by after semi-finished product deionized water centrifuge washing 3-5 times, (B, O) codope g-C is obtained within dry 24-36 hours3N4Photochemical catalyst.Compared with prior art, photo catalytic reduction Cr of the present invention6+Waste water it is high-efficient, preparation method is simple, and low in cost, be suitble to industrialization.
Description
Technical field
The invention belongs to Cr6+Catalytic reduction technique field, and in particular to one kind contains Cr for efficient process6+Waste water (B,
O) codope g-C3N4The preparation method of photochemical catalyst.
Background technique
Heavy metal pollution is most important pollution sources in China's water pollution, and chromium is exactly one of them.The chromium in water body
Element mainly has trivalent chromium (Cr (III) or Cr3+) and Cr VI (Cr (VI) or Cr6+) two kinds of existing ways.Wherein Cr VI is
The property swallowed poisonous substance/imbedibility poisonous substance, skin contact may cause sensitivity；It is more likely to cause inherited genetic defects, have to environment
Lasting risk.Cr VI is easy to be absorbed by the body, it can invade human body by digestion, respiratory tract, skin and mucous membrane.
It has been reported that having different degrees of hoarse, Atrophic nasal mucosas when by breathing the chromic anhybride in air containing various concentration, seriously
When can also make perforation of nasal septum and bronchiectasis etc..It can cause vomiting when being invaded through alimentary canal, abdomen pain.Meeting when being invaded through skin
Generate dermatitis and eczema.Excessive (more than 10ppm) Cr6+There is lethal effect to aquatic organism.Cr VI in contaminated drinking water
It can be carcinogenic.After animal drinks the water containing Cr VI, Cr VI can be absorbed by the cell of many tissues and organ in vivo.Thus may be used
See, hexavalent chromium is very big to the murder by poisoning of human health.Cr6+It is mainly derived from the discharge of the industries such as intermetallic composite coating, plating, tannery
Waste water and exhaust gas.And it is normally metabolic can to participate in body as microelement essential in body for trivalent chromium
Process, so using photo catalytic reduction Cr6+Have great importance.
2009 Nian Wangxin mornings et al. report g-C3N4Photochemical catalyst, find it have it is low in cost, nontoxic, have can
Many advantages, such as light-exposed activity and excellent thermal stability.In recent years, people are improving g-C3N4It is carried out in terms of photocatalytic activity
A large amount of research, has been summed up following several method.
The patent of application number 201811373180.2 discloses a kind of Three-element composite photocatalyst and preparation method and application.
C/g-C is made using saccharomycete as charcoal source for the invention3N4Carrier, and loaded Cu on this support2WS4It obtains having stronger light and urge
Change the Cu of performance2WS4/C/g-C3N4Composite photo-catalyst；The photochemical catalyst helps to improve the activity of catalyst, and utilization is visible
Light is excited, and is contacted with contaminant molecule, and catalysis or conversion effet are realized in interaction, swashs the oxygen of surrounding and hydrone
The free anion of great oxidizing force is sent out into, to achieve the purpose that harmful organic substances in degradation environment, this method will not be made
At the wasting of resources and the formation polluted is added, and easy to operate, cost is relatively low, is a kind of environmentally protective efficient process technology.
Although the catalyst prepares g-C by reactant of urea3N4, but final purpose is Cu in order to obtain2WS4/C/g-C3N4Ternary
Composite photo-catalyst, this Three-element composite photocatalyst preparation method is cumbersome, complex process, and needs strict control g-
C3N4With Cu2WS4Ratio between C three-phase, if ratio is improper, it is possible to reduce photocatalytic activity.
A kind of visible-light response type g-C of the patent disclosure of application number CN201810294291.83N4/ PDI photochemical catalyst and its
Preparation method and application.By by the g-C of low polymerization degree3N4It is compound with PMDA, it obtains a kind of photocatalysis performance and is much higher by g-
C3N4Catalyst (g-C3N4/ PDI), and it is applied to the conversion of As in water body (III) and Cr (VI).The catalyst can incite somebody to action
Oxygen selective reduction is H2O2, other than catalyst itself is to the conversion of As (III) and Cr (VI), the production of catalyst generation
Object can further convert As (III) and Cr (VI).Thus the visible light catalyst g-C of the prior art is solved3N4Handle As in water body
(III) and Cr (VI) catalytic efficiency is low and existing water body in As (III) and Cr (VI) lack the skill of effective treating method
Art problem.But the photochemical catalyst of the patent disclosure, at high cost, complex process, and the thermal stability of PDI is poor, limits
Its further practical application.
The patent of application number CN201310123137.1 discloses a type graphene C3N4Material and preparation method thereof and use
On the way.Preparation step is as follows: using dicyanodiamine in N2Synthesizing multilayer graphite mould C under atmosphere3N4(g-C3N4), by g-C3N4And NH4Cl
Solution mixing, is put into polytetrafluoro reaction kettle, carries out hydro-thermal reaction, is cooled to room temperature, and forms amination carbon nitride material；Again by amine
Change carbon nitride material and be put into tube furnace, is heat-treated, obtains class graphene C3N4Material.The present invention utilizes hydro-thermal, calcination processing
Method obtain single layer or few layer class graphene C3N4Material, such graphene C3N4Material has efficient, long-acting photocatalytic
Can, it can be applied to solar energy trans-utilization, environmental contaminants purification, detection of heavy metal ion, such as photolysis water hydrogen, organic dirt
Contaminate object degradation, Cr3+Etc. heavy metal ion analysis detection etc. in the environment.Although available single layer or few layer by this method
Class graphene C3N4Material, but the catalyst is related to N2Calcining, hydro-thermal under atmosphere are calcined again, and technique is more complex；
In addition, the class graphene C obtained by this method3N4Material is not involved with the regulation of electronic structure, photo-generate electron-hole
Pair recombination rate it is still very fast, cause photocatalytic activity still lower.
Application number CN201610413719.7 discloses a kind of MIL-53 (Fe)/g-C3N4Nanometer sheet composite photocatalyst material
Preparation method, belong to catalysis material preparation field.Firstly, being precursor, under the high temperature conditions copolyreaction using urea
Synthesize g-C3N4, and g-C is removed using ultrasonic method3N4Nanometer sheet is obtained, is then mixed with the predecessor of MIL-53 (Fe), it is molten
Agent thermal response obtains MIL-53 (Fe)/g-C3N4Nanosheet composite material.The catalyst photocatalytic activity is high, environmental-friendly, can
Recycling, and synthetic method is simple and convenient, and heavy metal Cr (VI) is dirty in the water that can efficiently degrade under visible light conditions
Object is contaminated, is had broad application prospects.But MIL-53 (Fe)/g-C3N4It is related in nanometer sheet composite photocatalyst material
MIL-53 (Fe) is a kind of MOF material, and often stability is poor in an aqueous medium for MOF material, limits it in actual waste water
Multiple circular treatment heavy metal Cr (VI) pollutant under environment.
Application number CN201610841631.5 discloses a kind of g-C3N4/Bi2O3/BiOI/TiO2Nanotube is visible light-responded
Photochemical catalyst electrode and its method of preparation and application, the preparation include the following steps: (1) configuration sodium hydroxide alcoholic solution B and contain
g-C3N4Five water bismuth nitrate ethylene glycol solution A, by TiO2NTs electrode alternately extracts in solution A and solution B, extracts every time
Washes of absolute alcohol afterwards；(2) it will be calcined under air atmosphere after the drying of step (1) the electrode obtained, distilled water flushing, wind after cooling
Do to obtain C3N4/Bi2O3/TiO2NTs electrode；(3) by C3N4/Bi2O3/TiO2NTs electrode immerses in KI ethanol water, takes out
It first air-dries afterwards, then in 70~90 DEG C of 8~12h of processing of constant temperature.The preparation method of electrode of the present invention is simple, it is seen that and photoresponse is strong,
It is obvious to the effect containing Cr (VI) wastewater treatment, it is without secondary pollution, it can be used for multiple times.But the catalyst is g-C3N4/
Bi2O3/BiOI/TiO2Four phase photochemical catalyst of nanotube, ingredient is more complex, and preparation process is cumbersome, and g-C3N4/Bi2O3/
BiOI/TiO2Ratio between four kinds of object phases of nanotube needs strict control, otherwise easily causes the reduction of photocatalytic activity.
Summary of the invention
For g-C in the prior art3N4Photo-generated carrier recombination rate height causes photocatalytic activity low and existing text
Offer with it is most of in patent be to pass through g-C3N4It is compound to improve g-C with other semiconductor materials3N4Photocatalytic activity exists
Complex process, high production cost need strict control g-C3N4The problems such as ratio between other semiconductor materials.The present invention
One kind is provided for efficient process containing Cr6+(B, O) the codope g-C of waste water3N4The preparation method of photochemical catalyst, this method are raw
Produce low in cost, and catalyst photo catalytic reduction Cr6+It is active high.
One kind containing Cr for efficient process6+(B, O) the codope g-C of waste water3N4The preparation method of photochemical catalyst, including with
Lower step:
Step 1, urea 8-12g, NaBH are weighed40.1g-0.8g, and by urea and NaBH4It is put into mortar, grinds 10-
30min makes two components be uniformly mixed to obtain mixture A；
Step 2, mixture A is put into crucible, and closed the lid, be placed in Muffle furnace and calcine 1-3 hours, with furnace nature
After being cooled to room temperature, semi-finished product are taken out；
Step 3, by after semi-finished product deionized water centrifuge washing 3-5 times, (B, O) codope g- is obtained within dry 24-36 hours
C3N4Photochemical catalyst.
It is urea and NaBH in step 1 as improved4Mass ratio be 25:1.
It is the heating rate calcined in step 2 as improved is 3-7 DEG C/min, calcination temperature is 500-600 DEG C.
Further improved to be, the heating rate calcined in step 2 is 5 DEG C/min, and calcination temperature is 550 DEG C.
It is that dry temperature is 60-100 DEG C in step 3 as improved.
Reaction principle: the present invention is first by urea and NaBH4Mixed grinding makes it be uniformly mixed (step 1)；Again in urea
Along with NaBH in high-temperature calcination polycondensation process4Decomposition and release (step 2) so that NaBH4In B atom indentation arrive
Urea polycondensation reacts the g-C to be formed3N4In seven piperazine ring frames of structure, so that the doping of B atom is realized, in addition, since reaction is
It is carried out in the Muffle furnace of no inert gas atmosphere protection, while NaBH4Decomposition and release can generate NaH, and NaH is chemical
Reactivity is very high, easily captures the O atom of oxygen in air, so that in NaBH4Modified g-C3N4O is former in sample
Son can enter g-C3N4In seven piperazine ring frames of structure, the doping of O atom is realized, it can be seen that, NaBH is added4It is modified, it can be real
The codope of existing (B, O) atom；Finally by with deionized water 3-5 (step 3) of centrifuge washing, remaining Na can be removed+,
(B, O) codope g-C is obtained after drying3N4Photochemical catalyst.
Above-mentioned photochemical catalyst is in photo catalytic reduction Cr6+On application when, with pure g-C3N4It compares, (B, O) codope g-
C3N4Photochemical catalyst realizes the regulation (as shown in 3 interpretation of result of embodiment) of microscopic appearance and electronic structure, so that its light
Catalysis reduction Cr6+Ability is stronger.
The utility model has the advantages that
Compared with prior art, remarkable advantage of the invention is:
(1) compared with prior art, method provided by the invention does not both need the surfactant that addition is additional, expensive
Or template, it does not need compound with other semiconductor materials yet, has many advantages, such as that production cost is low, simple process；
(2) NaBH is added in the invention patent discovery4The codope of (B, O) two kinds of elements may be implemented, it is, in principle, that tool
There is certain novelty.This is because along with NaBH in urea high-temperature calcination polycondensation process4Decomposition and release so that
NaBH4In B atom indentation the g-C to be formed is reacted to urea polycondensation3N4In seven piperazine ring frames of structure, to realize B atom
Doping, in addition, due to reacting carried out in the Muffle furnace of no inert gas atmosphere protection, while NaBH4Decomposition and release
NaH can be generated by putting, and NaH chemical reactivity is very high, easily captures the O atom of oxygen in air, so that in NaBH4Change
G-C after property3N4O atom can enter g-C in sample3N4In seven piperazine ring frames of structure, the doping (atomic percent of O atom is realized
Number is about 13.24%).And it is being added without NaBH4Under conditions of, that obtain is pure g-C3N4, only contain micro O element (atom
3.25%) percentage is about.It can be seen that NaBH is added4The doping of B element not only may be implemented, can also be reacted by changing
Environment and approach cause the doping of O element；
(3) prepared by the method optimal proportion (i.e. urea and NaBH4Mass ratio be 25:1) (B, O) codope
g-C3N4Photochemical catalyst photo catalytic reduction Cr in 200min6+Removal rate reaches as high as 97%, and obtained by conventional method
Pure g-C3N4Under the same conditions, photo catalytic reduction Cr6+Removal rate only has 16%.It can be seen that the side provided through the invention
Method can increase substantially g-C3N4Photo catalytic reduction Cr6+Performance；
(4) with pure g-C3N4Compare, optimal proportion (i.e. urea and NaBH4Mass ratio be 25:1) (B, O) codope
g-C3N4Photochemical catalyst sample density of photocurrent average value improves about 3 times, and can see in electrochemical AC impedance map
Optimal proportion (i.e. urea and NaBH out4Mass ratio be 25:1) (B, O) codope g-C3N4Photochemical catalyst sample arc radius
Reduce.This explanation, (B, O) codope g-C3N4The separation of photochemical catalyst sample photo-generated carrier and transport efficiency are remarkably reinforced.
Detailed description of the invention
Fig. 1 is the XRD spectrum of catalyst prepared by comparative example 1 of the present invention and different embodiments, wherein (a) be comparative example 1,
(b) be embodiment 1, (c) be embodiment 2, (d) is embodiment 3, (e) is embodiment 4；
Fig. 2 is the TEM figure of catalyst prepared by comparative example 1 and different embodiments, wherein (a) is pair that scale is 200nm
1 catalyst of ratio, (b) be scale be 100nm 1 catalyst of comparative example, (c) be scale be 200mm 3 catalyst of embodiment,
(d) it is 3 catalyst of embodiment that scale is 100nm；
Fig. 3 is the full spectrogram of XPS of catalyst prepared by comparative example 1 and embodiment 3, wherein (a) is the catalysis of comparative example 1
Agent, the catalyst that (b) is embodiment 3；
Fig. 4 (A) is the high-resolution XPS spectrum figure of C 1s, wherein (a) is comparative example 1, (b) is embodiment 3；
Fig. 4 (B) is the high-resolution XPS spectrum figure of N 1s, wherein (a) is comparative example 1, (b) is embodiment 3；
Fig. 4 (C) is the high-resolution XPS spectrum figure of O 1s, wherein (a) is comparative example 1, (b) is embodiment 3；
Fig. 4 (D) is the high-resolution XPS spectrum figure of the B 1s of catalyst prepared by embodiment 3；
Fig. 5 is high-resolution valence band XPS spectrum figure, wherein (a) is comparative example 1, (b) is embodiment 3；
Fig. 6 is the FTIR figure of catalyst prepared by comparative example 1 and different embodiments, wherein (a) is comparative example 1, (b) is
Embodiment 1, (c) are embodiment 2, (d) is embodiment 3, (e) is embodiment 4；
Fig. 7 is under the radiation of visible light of λ > 420nm, and the catalyst of comparative example 1 and the preparation of different embodiments is in photocatalysis
Restore Cr6+Effect picture, (a) is comparative example 1, (b) is embodiment 1, (c) is embodiment 2, (d) is embodiment 3, (e) is real
Apply example 4；
Fig. 8 is photocurrent response curve (I-t) figure of catalyst prepared by comparative example 1 and embodiment 3, wherein (a) is pair
The catalyst of ratio 1, the catalyst that (b) is embodiment 3；
Fig. 9 is electrochemical AC impedance (EIS) figure of catalyst prepared by comparative example 1 and embodiment 3, wherein (a) is pair
The catalyst of ratio 1, the catalyst that (b) is embodiment 3.
Specific embodiment
The invention will be further described in the following with reference to the drawings and specific embodiments.
Comparative example 1
Firstly, weighing 10g urea with electronic analytical balance, it is added without NaBH4, put it into 100ml crucible, close the lid
Son and in Muffle furnace with the heating rate of 5 DEG C/min, 2h is calcined in 550 DEG C of high temperature, after furnace cooled to room temperature
Take out sample.By sample with deionized water centrifuge washing 3 times, it is put into drying box 60 DEG C of dryings for 24 hours, final collection catalyst.
XRD spectra (Fig. 1 (a)) show the sample of pure urea preparation there are two characteristic peak, out peak position at 27.6 ° and
13.2 °, strongest diffraction peak is in 27.6 °, with g-C3N4(002) crystal face be consistent；13.2 ° of diffraction maximum and g-C3N4's
(100) crystal face is consistent.TEM figure, i.e. Fig. 2 (a)-Fig. 2 (b) show pure g-C3N4Show the lamellar structure of fold.The full spectrogram of XPS
(Fig. 3 (a)) shows pure g-C3N4C element (atomic percentage is about 44.67%) and N element (atomic percent are mainly contained in sample
About 52.08%) number, also contains a small amount of O element (atomic percentage is about 3.25%).C 1s high-resolution XPS spectrum figure (Fig. 4
(A) (a) curve in) show pure g-C3N4C 1s can fit 3 peaks in sample, and the peak at 284.8eV belongs to C-C key,
Small peak belongs to C=N key at 286.4eV, and the strong peak at 288.1eV belongs to C-N key.N 1s high-resolution XPS spectrogram
((a) curve in Fig. 4 (B)) shows pure g-C3N4N 1s can fit 3 peaks in sample, and the peak at 398.6eV belongs to two coordinations
N atom (N2c, i.e. C=N-C key), the peak at 399.5eV belongs to the N atom (N of three-fold coordination3c, i.e. N- (C)3Group),
Peak at 401.1eV belongs to g-C3N4The N-H group of seven piperazine ring frames in structure.Faint O 1s high-resolution XPS spectrum figure (figure
(a) curve in 4 (C)) show pure g-C3N4Contain only micro O element in sample, faint peak belongs to C-O at 532.1eV
Key.High-resolution valence band XPS spectrum figure (Fig. 5 (a)) shows pure g-C3N4The top of valence band position of sample is 1.24eV.FTIR spectrum (Fig. 6
(a)) show pure g-C3N4Sample is in 3450cm-1The peak at place belongs to the flexible vibration of O-H caused by the micro-moisture contained in sample
It is dynamic, in 1620cm-1The peak at place belongs to g-C3N4C=N vibration absorption peak in sample, in 1250cm-1The peak at place belongs to g-
C3N4C-N vibration absorption peak in sample, in 810cm-1The peak at place belongs to g-C3N4N-C=N vibration absorption peak in sample.
Photo catalytic reduction Cr6+Fig. 7 (a) shows pure g-C3N4Sample is after radiation of visible light 200min, photo catalytic reduction Cr6+Removal rate
It is 16%.Shown in photoelectric current test result such as Fig. 8 (a), it can be seen that pure g-C3N4Sample density of photocurrent average value is about
0.015μA·cm2, density of photocurrent value is smaller, this shows pure g-C3N4Sample photo-generate electron-hole is to separation and migration effect
It is poor.Shown in electrochemical alternate impedance spectrum such as Fig. 9 (a), it can be seen that pure g-C3N4Sample arc radius is larger, shows electrochemistry
AC impedance is larger, it means that pure g-C3N4Sample light induced electron migration effect is poor.
Embodiment 1
Firstly, weighing 10g urea with electronic analytical balance, then weigh the NaBH of 0.1g4(i.e. urea and NaBH4Mass ratio
It for 100:1), is put into mortar, grinding 20min is sufficiently mixed each component uniformly, then puts it into 100ml crucible, covers
Lid and in Muffle furnace with the heating rate of 5 DEG C/min, 2h is calcined in 550 DEG C of high temperature, with furnace cooled to room temperature
After take out sample.By sample with deionized water centrifuge washing 3 times, it is for 24 hours, final to collect catalysis to be put into 60 DEG C of dryings in drying box
Agent.
XRD spectra (Fig. 1 (b)) shows the NaBH for 0.1g is added4Modified g-C3N4, with g-C before modified3N4Phase
Than having lacked the corresponding diffraction maximum of (100) crystal face in XRD spectra, this is caused by Solute Content in Grain；And (002) crystal face institute
Corresponding diffraction maximum position is deviated to low-angle, this is because NaBH4Cause caused by element doping after modification.FTIR light
Spectrum (Fig. 6 (b)) shows the NaBH that 0.1g is added4Modified g-C3N4Sample is in 3450cm-1The peak at place, which belongs in sample, to be contained
O-H stretching vibration caused by some micro-moistures, in 2150cm-1The peak at place belongs to the C=O vibration absorption peak in sample, In
1620 cm-1The peak at place belongs to the C=N vibration absorption peak in sample, in 1250cm-1The peak at place belongs to the C-N in sample
Vibration absorption peak, in 1080cm-1The peak at place belongs to the N-B-O vibration absorption peak in sample, in 810cm-1The peak at place belongs to
N-C=N vibration absorption peak in sample.Photo catalytic reduction Cr6+Fig. 7 (b) shows the sample of the preparation of embodiment 1 in radiation of visible light
After 200min, photo catalytic reduction Cr6+Removal rate is 75%.
Embodiment 2
Firstly, weighing 10g urea with electronic analytical balance, then weigh the NaBH of 0.2g4(i.e. urea and NaBH4Mass ratio
It for 50:1), is put into mortar, grinding 20min is sufficiently mixed each component uniformly, then puts it into 100ml crucible, closes the lid
Son and in Muffle furnace with the heating rate of 5 DEG C/min, 2h is calcined in 550 DEG C of high temperature, after furnace cooled to room temperature
Take out sample.By sample with deionized water centrifuge washing 3 times, it is put into 60 DEG C of dryings in drying box and for 24 hours, finally collects sample.
XRD spectra (Fig. 1 (c)) shows the NaBH for 0.2g is added4Modified g-C3N4, with g-C before modified3N4Phase
Than having lacked the corresponding diffraction maximum of (100) crystal face in XRD spectra, this is caused by Solute Content in Grain；And (002) crystal face institute
Corresponding diffraction maximum position is deviated to low-angle, this is because NaBH4Cause caused by element doping after modification.FTIR light
Spectrum (Fig. 6 (c)) shows the NaBH that 0.2g is added4Modified g-C3N4Sample is in 3450cm-1The peak at place, which belongs in sample, to be contained
O-H stretching vibration caused by some micro-moistures, in 2150cm-1The peak at place belongs to the C=O vibration absorption peak in sample, In
1620 cm-1The peak at place belongs to the C=N vibration absorption peak in sample, in 1400cm-1The peak at place belongs to the B-N in sample
Vibration absorption peak, in 1250cm-1The peak at place belongs to the C-N vibration absorption peak in sample, in 1080cm-1The peak at place belongs to
N-B-O vibration absorption peak in sample, in 810cm-1The peak at place belongs to the N-C=N vibration absorption peak in sample.Photocatalysis is also
Former Cr6+Fig. 7 (c) show embodiment 2 prepare sample after radiation of visible light 200min, photo catalytic reduction Cr6+Removal rate is
80%.
Embodiment 3
Firstly, weighing 10g urea with electronic analytical balance, then weigh the NaBH of 0.4g4(i.e. urea and NaBH4Mass ratio
It for 25:1), is put into mortar, grinding 20min is sufficiently mixed each component uniformly, then puts it into 100ml crucible, closes the lid
Son and in Muffle furnace with the heating rate of 5 DEG C/min, 2h is calcined in 550 DEG C of high temperature, after furnace cooled to room temperature
Take out sample.By sample with deionized water centrifuge washing 3 times, it is put into 60 DEG C of dryings in drying box and for 24 hours, finally collects sample.
XRD spectra (Fig. 1 (d)) shows the NaBH for 0.4g is added4Modified g-C3N4, with g-C before modified3N4Phase
Than having lacked the corresponding diffraction maximum of (100) crystal face in XRD spectra, while the corresponding diffraction of (101) crystal face nearby occur at 43 °
Peak, this is caused by Solute Content in Grain；And (002) diffraction maximum position corresponding to crystal face to low-angle deviate, this be by
In NaBH4Cause caused by element doping after modification.TEM figure (Fig. 2 (c)-Fig. 2 (d)) shows that NaBH is added4After modification
G-C3N4Show lamellar structure, fold disappears, and layer structure is more gentle, and the active site for being so catalyzed reaction increases
Add, is conducive to light-catalyzed reaction.The full spectrogram of XPS (Fig. 3 (b)) shows that NaBH is added4G-C after modification3N4It is main in sample
Containing C element (atomic percentage is about 27.68%) and N element (atomic percentage is about 34.69%), also containing a certain amount of
O element (atomic percentage is about 13.24%) and B element (atomic percentage is about 24.39%).C 1s high-resolution XPS spectrogram
((b) curve in Fig. 4 (A)) shows that NaBH is added4G-C after modification3N4C 1s can fit 3 peaks, 284.8eV in sample
The peak at place belongs to C-C key, and small peak belongs to C=N key at 286.4eV, and the strong peak at 288.4eV belongs to C-N key；Separately
Outside, with pure g-C3N4Peak in sample at 288.1eV is compared, and NaBH is added4G-C after modification3N4Sample goes out at 288.4eV
Peak, this movement to high combination energy direction is since the presence of O element leads to offset caused by C=O key.N 1s high-resolution
XPS spectrum figure ((b) curve in Fig. 4 (B)) shows that NaBH is added4G-C after modification3N4N 1s can fit 3 peaks in sample,
Peak at 398.6eV belongs to the N atom (N of two coordinations2c, i.e. C=N-C key), the peak at 400.1 eV belongs to the N of three-fold coordination
Atom (N3c, i.e. N- (C)3Group), the peak at 400.9eV belongs to g-C3N4The N-H group of seven piperazine ring frames in structure；In addition,
With pure g-C3N4Peak in sample at 399.5eV is compared, and NaBH is added4G-C after modification3N4Sample appearance at 400.1eV,
This movement to high combination energy direction is since the presence of B element leads to offset caused by B-N key.O 1s high-resolution XPS spectrum
Figure ((b) curve in Fig. 4 (C)) shows that NaBH is added4G-C after modification3N4Contain O element, the peak at 532.1eV in sample
C=O key is belonged to, the peak at 533.2eV belongs to B-O key.B 1s high-resolution XPS spectrum figure (Fig. 4 (D)) shows that NaBH is added4
G-C after modification3N4B1s can fit 2 peaks in sample, and the peak at 190.7eV belongs to B-N key, the peak at 191.5eV
Belong to B-O key (J.Am.Chem.Soc.2011,133,7121-7127；Adv.Mater.2017,29,1605148；ACS
Nano 2018,129,9441-9450).High-resolution valence band XPS spectrum figure (Fig. 5 (b)) shows and pure g-C3N4The top of valence band of sample
(1.24eV) is compared for position, and NaBH is added4G-C after modification3N4The top of valence band position of sample is 1.60eV, shows to be added
NaBH4G-C after modification3N4The top of valence band of sample is corrected.FTIR spectrum (Fig. 6 (d)) shows the NaBH that 0.4g is added4It is modified
G-C afterwards3N4Sample is in 3450cm-1The peak at place belongs to O-H stretching vibration, In caused by the micro-moisture contained in sample
2150cm-1The peak at place belongs to the C=O vibration absorption peak in sample, in 1620cm-1The peak at place belongs to the C=N in sample
Vibration absorption peak, in 1400cm-1The peak at place belongs to the B-N vibration absorption peak in sample, in 1080cm-1The peak at place belongs to
N-B-O vibration absorption peak in sample, in 800cm-1The peak at place belongs to the B-N-B vibration absorption peak in sample
(J.Am.Chem.Soc.2011,133, 7121–7127；The synthesis and Research of Spectrum Characteristics of nanoscale BCNO is gone into business small
Wave).Photo catalytic reduction Cr6+Fig. 7 (d) show embodiment 3 prepare sample after radiation of visible light 200min, photo catalytic reduction
Cr6+Removal rate is 97%.Sample made from the example restores Cr6+Effect is best.Fig. 8 shows the pure g- prepared with comparative example 1
C3N4(density of photocurrent average value is about 0.015 μ Acm2) compare, the NaBH that embodiment 3 passes through addition 0.4g4Preparation
(B, O) codope g-C3N4Photochemical catalyst sample density of photocurrent average value (about 0.05 μ Acm2) about 3 times are improved, table
Bright (B, O) codope g-C3N4Photochemical catalyst photo-generate electron-hole enhances separative efficiency, and light induced electron transport efficiency obtains
To raising；Fig. 9 shows in electrochemical AC impedance map, compared to the pure g-C of the preparation of comparative example 13N4, embodiment 3 is by adding
Add the NaBH of 0.4g4(B, O) the codope g-C of preparation3N4Photochemical catalyst sample arc radius reduces, and illustrates (B, O) codope g-
C3N4Photochemical catalyst can be effectively reduced interfacial resistance, improve electric charge transfer rate.In short, Fig. 8 and Fig. 9 result all illustrates,
Add NaBH4(B, O) the codope g-C of preparation3N4The separation of photochemical catalyst sample photo-generated carrier and transport efficiency are obviously increased
By force.
Embodiment 4
Firstly, weighing 10g urea with electronic analytical balance, then weigh the NaBH of 0.8g4(i.e. urea and NaBH4Mass ratio
It for 12.5:1), is put into mortar, grinding 20min is sufficiently mixed each component uniformly, then puts it into 100ml crucible, covers
Lid and in Muffle furnace with the heating rate of 5 DEG C/min, 2h is calcined in 550 DEG C of high temperature, with furnace cooled to room temperature
After take out sample.By sample with deionized water centrifuge washing 3 times, it is for 24 hours, final to collect finished product light to be put into 60 DEG C of dryings in drying box
Catalyst.
XRD spectra (Fig. 1 (e)) shows the NaBH for 0.8g is added4Modified g-C3N4, with g-C before modified3N4Phase
Than having lacked the corresponding diffraction maximum of (100) crystal face in XRD spectra, while the corresponding diffraction of (101) crystal face nearby occur at 43 °
Peak, this is caused by Solute Content in Grain；And (002) diffraction maximum position corresponding to crystal face to low-angle deviate, this be by
In NaBH4Cause caused by element doping after modification.FTIR spectrum (Fig. 6 (e)) shows the NaBH that 0.8g is added4It is modified
G-C3N4Sample is in 3450cm-1The peak at place belongs to O-H stretching vibration, In caused by the micro-moisture contained in sample
2150cm-1The peak at place belongs to the C=O vibration absorption peak in sample, in 1620cm-1The peak at place belongs to the C=N in sample
Vibration absorption peak, in 1400cm-1The peak at place belongs to the B-N vibration absorption peak in sample, in 1080cm-1The peak at place belongs to
N-B-O vibration absorption peak in sample, in 800cm-1The peak at place belongs to the B-N-B vibration absorption peak in sample.Photocatalysis is also
Former Cr6+Fig. 7 (e) show embodiment 4 prepare sample after radiation of visible light 200min, photo catalytic reduction Cr6+Removal rate is
88%.
Preparation method of the present invention is by by urea and NaBH4High-temperature calcination after mixing, then, success dry by centrifuge washing
Obtain (B, O) codope g-C3N4Photochemical catalyst；NaBH is proposed from principle4Work in terms of realization (B, O) codope
With；It was found that method provided by the invention can increase substantially g-C3N4Photo catalytic reduction Cr6+Performance: optimal proportion is (i.e.
Urea and NaBH4Mass ratio be 25:1) (B, O) codope g-C3N4Photochemical catalyst photo catalytic reduction Cr in 200min6+It goes
Except rate reaches as high as 97%, and the pure g-C obtained by conventional method3N4Under the same conditions, photo catalytic reduction Cr6+Removal rate
Only 16%；With pure g-C3N4Compare, optimal proportion (i.e. urea and NaBH4Mass ratio be 25:1) (B, O) codope g-
C3N4The separation of photochemical catalyst sample photo-generated carrier and transport efficiency are remarkably reinforced.Compared with prior art, the present invention is catalyzed
High-efficient, preparation method is simple, and low in cost, is suitble to industrialization.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not limited to this hair the foregoing is merely a specific embodiment of the invention
Bright, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the present invention
Protection scope within.
Claims (5)
1. one kind contains Cr for efficient process6+(B, O) the codope g-C of waste water3N4The preparation method of photochemical catalyst, feature exist
In, comprising the following steps: step 1, weigh urea 8-12g, NaBH40.1g-0.8g, and by urea and NaBH4It is put into mortar,
Grinding 10-30min makes two components be uniformly mixed to obtain mixture A；Step 2, mixture A is put into crucible, and closed the lid,
It is placed in Muffle furnace and calcines 1-3 hours, after furnace cooled to room temperature, take out semi-finished product；Step 3, by semi-finished product spend from
After sub- water centrifuge washing 3-5 times, (B, O) codope g-C is obtained within dry 24-36 hours3N4Photochemical catalyst.
2. a kind of efficient process that is used for according to claim 1 contains Cr6+(B, O) the codope g-C of waste water3N4Photochemical catalyst
Preparation method, which is characterized in that urea and NaBH in step 14Mass ratio be 25:1.
3. a kind of efficient process that is used for according to claim 1 contains Cr6+(B, O) the codope g-C of waste water3N4Photochemical catalyst
Preparation method, which is characterized in that the heating rate calcined in step 2 be 3-7 DEG C/min, calcination temperature be 500-600 DEG C.
4. a kind of efficient process that is used for according to claim 3 contains Cr6+(B, O) the codope g-C of waste water3N4Photochemical catalyst
Preparation method, which is characterized in that the heating rate calcined in step 2 be 5 DEG C/min, calcination temperature be 550 DEG C.
5. a kind of efficient process that is used for according to claim 1 contains Cr6+(B, O) the codope g-C of waste water3N4Photochemical catalyst
Preparation method, which is characterized in that dry temperature is 60-100 DEG C in step 3.
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| CN113522338A (en) * | 2021-07-19 | 2021-10-22 | 武汉纺织大学 | Boron-oxygen co-doped carbon nitride non-metallic ozone catalyst and preparation method and application thereof |
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| CN114225956A (en) * | 2021-12-29 | 2022-03-25 | 南京大学环境规划设计研究院集团股份公司 | Preparation method and application of composite photocatalytic material for degrading antibiotics and hexavalent chromium |
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