CN109894126A - A kind of preparation method of the BiOX fixed nitrogen photochemical catalyst of three-dimensional structure - Google Patents
A kind of preparation method of the BiOX fixed nitrogen photochemical catalyst of three-dimensional structure Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of the BiOX fixed nitrogen photochemical catalyst of three-dimensional structure, include the following steps: that (1) configures glucose solution；(2) hydro-thermal reaction, washing, is centrifuged and dries；(3) it is placed in acetic acid aqueous solution, magnetic agitation；(4) Bi (NO is added3)3·5H2O obtains tan precipitate until adding the halogeno salt of same molar after being completely dissolved；(5) BiOX photocatalyst of three-dimensional structure is obtained after dry, calcining.The various fixed nitrogen photochemical catalysts prepared by template of the invention, preparation process is simple, and low energy consumption, simultaneously, three-dimensional structure sample can be prepared respectively using different halogeno salts, and product purity is high, pattern is uniform, good dispersion, performance are stablized, and cycle performance is excellent.
Description
Technical field
The present invention relates to a kind of preparation method of photocatalysis fixed nitrogen catalyst, specially a kind of BiOX of three-dimensional structure
The preparation method of fixed nitrogen photochemical catalyst belongs to new energy materials preparation field.
Background technique
Ammonia is important one of inorganic chemical product, is with a wide range of applications.Urea, the phosphorus not only agriculturally used
Sour ammonium and the various synthesis containing nitrogen composite fertilizer are required using ammonia as raw material；And among industrial common nitrogenous and organic matter
Body, sulfa drug, polyurethane and Fypro etc. all need to be using ammonia as raw material；In addition, ammonia is synthesis trinitrotoluene, nitrify sweet
The important source material of common used material in the national defense industry such as oil, nitrocellulose.As agricultural, industry and national defence develop, whole world ammonia
Demand has reached nearly hundred million tons.
Currently, chemical industry fixed nitrogen and biological nitrogen fixation are to synthesize the main path of ammonia.Chemical industry fixed nitrogen solves biological nitrogen fixation not
Foot, but its at high cost, long flow path, energy consumption is high, environmental pollution is serious.Biological nitrogen fixation can carry out under the conditions of relatively mild, but only
Occur in a small number of plants and microorganism, it is difficult to realize large-scale production.Therefore, a kind of green cleaning is found, low energy consumption is consolidated
Nitrogen technology replaces existing nitrogen fixation technology to have important practical significance.
Photocatalysis fixed nitrogen is a kind of fixed nitrogen new technology that nitrogen is converted to ammonification using solar energy and semiconductor light-catalyst.
The advantages that can reusing because of its energy saving, environmentally protective, mild condition, catalyst, potentiality pole attracts attention, by each
The great attention of government, state and research circle.The critical issue of photocatalysis fixed nitrogen is the activation of tri- key of N ≡ N, allows N2Activation this
Kind material can be noble metal or the oxide rich in electronics.In view of the cost problem of noble metal, the oxide of electron rich
First choice as catalyst.When forming oxide, the lone pair electrons contained on bismuth atom are often not involved in into bismuth (Bi) element
It builds, becomes electron rich compound.Accordingly, it is considered to introduce bismuth ion in catalysis material preparation process, the oxygen of bismuth is generated
Compound catalysis material plays activation N2Effect.Therefore, bismuth-containing and the catalysis with excellent photocatalysis fixed nitrogen performance are prepared
Agent has become the urgent need in photocatalysis fixed nitrogen field.
Summary of the invention
In view of the above-mentioned problems of the prior art, the object of the present invention is to provide a kind of BiOXs of three-dimensional structure to consolidate
The preparation method of nitrogen photochemical catalyst, it is solid to prepare efficient bismuth-containing by mild reaction condition and shirtsleeve operation step
Nitrogen catalyst, although the halogeno salt being added is different, the finished catalyst of preparation all has three-dimensional structure；Meanwhile by changing
Kind preparation process obtains the product that pattern is more uniform and stability is more excellent to improve product purity.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of preparation method of the BiOX fixed nitrogen photochemical catalyst of three-dimensional structure, includes the following steps:
(1) it weighs a certain amount of glucose to be placed in deionized water, uniform glucose solution is obtained after magnetic agitation；
(2) glucose solution of step (1) is transferred in reaction kettle, carries out hydro-thermal reaction, then hydro-thermal is anti-
The product answered uses deionized water and ethanol washing respectively, is centrifuged and dries, obtains carbonaceous mesophase spherules；
(3) carbonaceous mesophase spherules obtained in step (2) are placed in acetic acid aqueous solution, magnetic agitation makes it
Even dispersion；
(4) Bi (NO is added into step (3) obtained solution3)3·5H2O, until adding identical rub after being completely dissolved
Tan precipitate is obtained after the halogeno salt of your amount, magnetic agitation and standing；
(5) BiOX of three-dimensional structure is obtained after the tan precipitate obtained in step (4) is dry, calcining
Photochemical catalyst.
Further, the halogeno salt in step (4) is selected from KI, NH4Cl、NH4One of Br.
It is furthermore preferred that glucose and the mass ratio of deionized water are between 1:8~1:12 range in step (1).
It is furthermore preferred that in step (2) hydro-thermal reaction condition are as follows: 60ml glucose solution is put into 100ml reaction kettle, temperature
160~200 DEG C of degree, 10~16h of soaking time.
It is furthermore preferred that the centrifugal condition in step (2) are as follows: centrifugal rotational speed is 6000 turns/min, and centrifugation time 5min is washed
Washing and be centrifuged number is 4 times.
It is furthermore preferred that the drying condition in step (2) are as follows: drying temperature is 60 DEG C, and drying time is for 24 hours.
It is furthermore preferred that the amount of carbonaceous mesophase spherules used in step (3) is 0.3~0.5g, the concentration of acetic acid is 1~
2mol/L aqueous solution, BiNO3·5H2The amount of O is 0.01mol, and the amount of the KI used is 0.01mol, 80~120 DEG C of drying temperature.
It is furthermore preferred that the condition calcined in step (5) are as follows: 500 DEG C of temperature, 1~2 DEG C/min of heating rate, soaking time
For 2~3h.
The invention has the benefit that
1, the various fixed nitrogen photochemical catalysts prepared by template, preparation process is simple, and technological parameter is adjustable, and low energy consumption,
At low cost, product yield is high, meanwhile, use different halogeno salt KI, NH4Cl、NH4Br can prepare three-dimensional structure
Bi5O7I, the finished product of BiOCl, BiOBr.
2, fixed nitrogen photocatalyst product prepared by the present invention purity is high, pattern is uniform, good dispersion, and than current research heat
Point TiO2Catalyst is compared, and optical response range is wide, and the efficiency of solar energy utilization is higher.
3, the Bi prepared by the present invention5O7I, BiOCl and BiOBr photochemical catalyst produces the rate point of ammonia after light reaction 3h
It Wei not 373.3 μm of ol g-1h-1、810μmol g-1h-1With 363.3 μm of ol g-1h-1, all it is far longer than TiO2Production ammonia rate
(0.83μmol g-1h-1)；Inventive can be stablized, and cycle performance is excellent, before having great commercial applications in terms of the fixed nitrogen
Scape.
Detailed description of the invention
Fig. 1 is the three-dimensional hollow Bi prepared under the conditions of embodiment 15O7The XRD diagram of I photocatalysis fixed nitrogen catalyst；
Fig. 2 is the three-dimensional hollow Bi prepared under the conditions of embodiment 15O7The SEM of I photocatalysis fixed nitrogen catalyst schemes；
Fig. 3 is the three-dimensional hollow Bi prepared under the conditions of embodiment 15O7I photochemical catalyst fixed nitrogen produces ammonia rate and time relationship
Figure；
Fig. 4 is the three-dimensional hollow Bi prepared under the conditions of embodiment 15O7I photocatalysis fixed nitrogen catalyst circulation uses production ammonia rate
Figure；
Fig. 5 is the XRD of the rose-shaped BiOCl photocatalysis fixed nitrogen catalyst prepared under the conditions of embodiment 4；
Fig. 6 schemes for the SEM of the rose-shaped BiOCl photocatalysis fixed nitrogen catalyst prepared under the conditions of embodiment 4；
Fig. 7 changes over time figure for the rose-shaped BiOCl catalyst fixed nitrogen production ammonia rate prepared under the conditions of embodiment 4；
Fig. 8 is to produce ammonia rate diagram under the rose-shaped BiOCl catalyst difference access times that prepare under the conditions of embodiment 4；
Fig. 9 is the XRD diagram of the three-dimensional hollow BiOBr photocatalysis fixed nitrogen catalyst prepared under the conditions of embodiment 7；
Figure 10 is the SEM figure of the three-dimensional hollow BiOBr photocatalysis fixed nitrogen catalyst prepared under the conditions of embodiment 7；
Figure 11 is that the three-dimensional hollow BiOBr catalyst fixed nitrogen prepared under the conditions of embodiment 7 produces ammonia rate and changes over time figure；
Figure 12 is that ammonia rate diagram is produced under the three-dimensional hollow BiOBr catalyst difference access times prepared under the conditions of embodiment 7.
Specific embodiment
Invention is further described in detail combined with specific embodiments below.
The halogeno salt that embodiment 1 to embodiment 3 is selected is KI, and the photochemical catalyst ingredient being prepared is Bi5O7I。
Embodiment 1:
A kind of three-dimensional hollow photocatalysis fixed nitrogen catalyst Bi5O7The preparation method of I, includes the following steps:
(1) glucose for weighing 5g is placed in the deionized water of 60ml, and it is water-soluble that uniform glucose is obtained after magnetic agitation
Liquid；
(2) glucose solution of step (1) is transferred in the reaction kettle of 100ml, 180 DEG C at a temperature of into
Row hydro-thermal reaction 12h, then the product of hydro-thermal reaction is used into deionized water and ethanol washing respectively, in 6000 turns/min, centrifugation
Between be centrifuged under conditions of 5min 4 times, then dried for 24 hours in 60 DEG C of temperature, obtain carbonaceous mesophase spherules；
(3) by the carbonaceous mesophase spherules obtained in step (2) weigh 0.5g be placed in fill 200ml, concentration is
In the acetic acid aqueous solution beaker of 1.5mol/L, then magnetic agitation keeps its evenly dispersed；
(4) Bi (NO of 0.02mol is added into step (3) obtained solution3)3·5H2O, until adding again after being completely dissolved
Enter the KI of 0.02mol, obtains tan precipitate after magnetic agitation 12h and standing；
(5) tan precipitate obtained in step (4) is dried to 12h under the conditions of 80 DEG C, and with temperature for 500
DEG C, heating rate is 2 DEG C/min, and soaking time arrives three-dimensional hollow Bi with calcining to drying precipitate for 2h5O7I catalysis
Agent.
To above-mentioned Bi5O7The photocatalysis fixed nitrogen performance test of I catalyst: three-dimensional hollow Bi obtained by 5mg is taken5O7I catalyst is put
Enter to filling 100ml, in the HCl solution reaction tube that concentration is 0.00005mol/L, and ultrasonic disperse.Reaction tube is sealed, with
0.05ml/min flow velocity is continually fed into nitrogen 30min.Later by reaction tube under the conditions of being protected from light magnetic agitation 30min, make to be catalyzed
Agent surface is to dilute hydrochloric acid and N2Reach adsorption-desorption balance.3h is irradiated using the xenon lamp of 300W as light source, is taken among it every lh
The reaction solution of 2ml is centrifuged, and a certain amount of ion chromatography solution is added；Based on Beer law, ultraviolet-visible spectrophotometer is utilized
Test the NH in photoreactive solution4 +Concentration, and then assess the fixed nitrogen performance of catalyst.The photocatalysis fixed nitrogen performance of this sample is as schemed
Shown in 3 and Fig. 4.
Embodiment 2:
A kind of three-dimensional hollow photocatalysis fixed nitrogen catalyst Bi5O7The preparation method of I, includes the following steps:
(1) glucose for weighing 3g is placed in the deionized water of 30ml, and it is water-soluble that uniform glucose is obtained after magnetic agitation
Liquid；
(2) glucose solution of step (1) is transferred in the reaction kettle of 50ml, 180 DEG C at a temperature of into
Row hydro-thermal reaction 12h, then the product of hydro-thermal reaction is used into deionized water and ethanol washing respectively, in 6000 turns/min, centrifugation
Between be centrifuged under conditions of 5min 4 times, then dried for 24 hours in 60 DEG C of temperature, obtain carbonaceous mesophase spherules；
(3) by the carbonaceous mesophase spherules obtained in step (2) weigh 0.4g be placed in fill 120ml, concentration is
In the acetic acid aqueous solution beaker of 1.2mol/L, then magnetic agitation keeps its evenly dispersed；
(4) Bi (NO of 0.015mol is added into step (3) obtained solution3)3·5H2O, until after being completely dissolved again
The KI of 0.015ml is added, obtains tan precipitate after magnetic agitation 12h and standing；
(5) tan precipitate obtained in step (4) is dried to 12h under the conditions of 80 DEG C, and with temperature for 500
DEG C, heating rate is 2 DEG C/min, and soaking time arrives three-dimensional hollow Bi with calcining to drying precipitate for 2h5O7I catalysis
Agent.
To above-mentioned Bi5O7The photocatalysis fixed nitrogen performance test of I catalyst: three-dimensional hollow Bi obtained by 4mg is taken5O7I catalyst is put
Enter to filling 80ml, in the HCl solution reaction tube that concentration is 0.00005mol/L, and ultrasonic disperse.Reaction tube is sealed, with
0.05ml/min flow velocity is continually fed into nitrogen 30min.Later by reaction tube under the conditions of being protected from light magnetic agitation 30min, make to be catalyzed
Agent surface is to dilute hydrochloric acid and N2Reach adsorption-desorption balance.3h is irradiated using the xenon lamp of 300W as light source, is taken among it every lh
The reaction solution of 2ml is centrifuged.A certain amount of ion chromatography solution is added, is based on Beer law, utilizes ultraviolet-visible spectrophotometer
Test the NH in photoreactive solution4 +Concentration, and then assess the fixed nitrogen performance of catalyst.Test result shows that this sample has and real
Apply the same outstanding photocatalysis fixed nitrogen performance of example 1.
Embodiment 3:
A kind of three-dimensional hollow photocatalysis fixed nitrogen catalyst Bi5O7The preparation method of I, includes the following steps:
(1) glucose for weighing 6g is placed in the deionized water of 60ml, and it is water-soluble that uniform glucose is obtained after magnetic agitation
Liquid；
(2) glucose solution of step (1) is transferred in the reaction kettle of 100ml, 180 DEG C at a temperature of into
Row hydro-thermal reaction 12h, then the product of hydro-thermal reaction is used into deionized water and ethanol washing respectively, in 6000 turns/min, centrifugation
Between be centrifuged under conditions of 5min 4 times, then dried for 24 hours in 60 DEG C of temperature, obtain carbonaceous mesophase spherules；
(3) it the carbonaceous mesophase spherules obtained in step (2) is weighed into 0.3g is placed in and fill 60ml and concentration is
In the acetic acid aqueous solution of 1mol/L, then magnetic agitation keeps its evenly dispersed；
(4) Bi (NO of 0.01mol is added into step (3) obtained solution3)3·5H2O, until adding again after being completely dissolved
Enter the KI of 0.01mol, obtains tan precipitate after magnetic agitation 12h and standing；
(5) tan precipitate obtained in step (4) is dried to 12h under the conditions of 80 DEG C, and with temperature for 500
DEG C, heating rate is 1 DEG C/min, and soaking time arrives three-dimensional hollow Bi with calcining to drying precipitate for 2h5O7I catalysis
Agent.
To above-mentioned Bi5O7The photocatalysis fixed nitrogen performance test of I catalyst: three-dimensional hollow Bi obtained by 5mg is taken5O7I catalyst is put
Enter to filling 80ml, in the HCl solution reaction tube that concentration is 0.00005mol/L, and ultrasonic disperse.Reaction tube is sealed, with
0.05ml/min flow velocity is continually fed into nitrogen 30min.Later by reaction tube under the conditions of being protected from light magnetic agitation 30min, make to be catalyzed
Agent surface is to dilute hydrochloric acid and N2Reach adsorption-desorption balance.3h is irradiated using the xenon lamp of 300W as light source, is taken among it every lh
The reaction solution of 2ml is centrifuged.A certain amount of ion chromatography solution is added, is based on Beer law, utilizes ultraviolet-visible spectrophotometer
Test the NH in photoreactive solution4 +Concentration, and then assess the fixed nitrogen performance of catalyst.Test result shows that this sample has and real
Apply the same outstanding photocatalysis fixed nitrogen performance of example 1.
From the XRD diagram of Fig. 1 as can be seen that pre-prepared sample at 10.9 °, 13.4 °, 28.1 °, 31.1 °, 33 °,
Diffraction maximum at 33.4 °, 46 °, 46.2 °, 47.7 °, 53.4 °, 56 ° and 58 ° respectively corresponds Bi5O7I standard card (JCPDS
No.40-0548 (200)), (201) (312), (004), (204), (020), (604), (024), (224), (316), (912)
(624) thus crystal face infers that sample is pure Bi without discovery impurity peaks in map5O7I.In addition, can from the SEM figure of Fig. 2
To find out, the Bi of preparation5O7I catalyst is three-dimensional hollow flower-like structure and pattern is uniform.It is by porous Bi5O7I nanometer thin
Piece self assembly forms, and there are a large amount of defects for nano flake border surface.Its porous surface can increase its specific surface area, mention
It is high its to adsorption capacity for nitrogen；Electronics at hole and boundary defect can be transferred into the antibonding π track of absorption nitrogen molecular, into
And three key of nitrogen-nitrogen is weakened, and then have excellent catalytic properties the catalyst；In addition, the catalyst is in ultrasonic vibration for 24 hours
Afterwards, pattern does not have any variation, shows there is very strong structural stability, makes it have good recycling effect；It is followed
Ring is as shown in Fig. 4 using experimental result.It can be obtained by analyzing above, by three-dimensional hollow Bi made from the invention preparation method5O7I
Fixed nitrogen catalyst, not only reaction condition is mild, and preparation cost is low, and sample surface morphology is uniform, and photocatalysis fixed nitrogen is had excellent performance.
The halogeno salt that embodiment 4 to embodiment 7 is selected is NH4Cl, and the photochemical catalyst ingredient being prepared is BiOCl.
Embodiment 4:
A kind of preparation method of rose-shaped photocatalysis fixed nitrogen catalyst BiOCl, includes the following steps:
(1) glucose for weighing 5g is placed in the deionized water of 60ml, and it is water-soluble that uniform glucose is obtained after magnetic agitation
Liquid；
(2) glucose solution of step (1) is transferred in the reaction kettle of 100ml, 180 DEG C at a temperature of into
Row hydro-thermal reaction 12h, then the product of hydro-thermal reaction is used into deionized water and ethanol washing respectively, in 6000 turns/min, centrifugation
Between be centrifuged under conditions of 5min 4 times, then dried for 24 hours in 60 DEG C of temperature, obtain carbonaceous mesophase spherules；
(3) by the carbonaceous mesophase spherules obtained in step (2) weigh 0.5g be placed in fill 200ml, concentration is
In the acetic acid aqueous solution beaker of 1.5mol/L, then magnetic agitation keeps its evenly dispersed；
(4) Bi (NO of 0.02mol is added into step (3) obtained solution3)3·5H2O, until adding again after being completely dissolved
Enter the NH of 0.02mol4Tan precipitate is obtained after Cl, magnetic agitation 12h and standing；
(5) tan precipitate obtained in step (4) is dried to 12h under the conditions of 80 DEG C, and with temperature for 500
DEG C, heating rate is 2 DEG C/min, and soaking time is that 2h is catalyzed drying precipitate and calcining to get to rose-shaped BiOCl
Agent.
Photocatalysis fixed nitrogen performance test to above-mentioned BiOCl catalyst: rose-shaped BiOCl catalyst obtained by 5mg is taken to put
Enter into the hydrochloric acid reaction tube for the 60ml for filling 0.1mol/L concentration simultaneously ultrasonic disperse, is continually fed into confined reaction system
N2.By reaction tube under the conditions of being protected from light magnetic agitation 30min, make catalyst surface to dilute hydrochloric acid and N2It is flat to reach adsorption-desorption
Weighing apparatus.3h is irradiated using xenon lamp as light source, takes the reaction solution of 2ml to be centrifuged every l h among it.It is molten that a certain amount of ion chromatography is added
Liquid is based on Beer law, utilizes the NH in ultraviolet-visible spectrophotometer test photoreactive solution4 +Concentration, and then assess catalysis
The fixed nitrogen performance of agent.The photocatalysis fixed nitrogen performance of this sample is as shown in Figure 7 and Figure 8.
Embodiment 5:
A kind of preparation method of rose-shaped photocatalysis fixed nitrogen catalyst BiOCl, includes the following steps:
(1) glucose for weighing 3g is placed in the deionized water of 30ml, and it is water-soluble that uniform glucose is obtained after magnetic agitation
Liquid；
(2) glucose solution of step (1) is transferred in the reaction kettle of 50ml, 180 DEG C at a temperature of into
Row hydro-thermal reaction 12h, then the product of hydro-thermal reaction is used into deionized water and ethanol washing respectively, in 6000 turns/min, centrifugation
Between be centrifuged under conditions of 5min 4 times, then dried for 24 hours in 60 DEG C of temperature, obtain carbonaceous mesophase spherules；
(3) by the carbonaceous mesophase spherules obtained in step (2) weigh 0.4g be placed in fill 180ml, concentration is
In the acetic acid aqueous solution beaker of 1.2mol/L, then magnetic agitation keeps its evenly dispersed；
(4) Bi (NO of 0.015mol is added into step (3) obtained solution3)3·5H2O, until after being completely dissolved again
The NH of 0.015ml is added4Tan precipitate is obtained after Cl, magnetic agitation 12h and standing；
(5) tan precipitate obtained in step (4) is dried to 12h under the conditions of 80 DEG C, and with temperature for 500
DEG C, heating rate is 2 DEG C/min, and soaking time is that 2h is catalyzed drying precipitate and calcining to get to rose-shaped BiOCl
Agent.
Photocatalysis fixed nitrogen performance test to above-mentioned BiOCl catalyst: rose-shaped BiOCl catalyst obtained by 5mg is taken to put
Enter into the hydrochloric acid reaction tube for the 60ml for filling 0.1mol/L concentration simultaneously ultrasonic disperse, is continually fed into confined reaction system
N2.By reaction tube under the conditions of being protected from light magnetic agitation 30min, make catalyst surface to dilute hydrochloric acid and N2It is flat to reach adsorption-desorption
Weighing apparatus.3h is irradiated using xenon lamp as light source, takes the reaction solution of 2ml to be centrifuged every l h among it.It is molten that a certain amount of ion chromatography is added
Liquid is based on Beer law, utilizes the NH in ultraviolet-visible spectrophotometer test photoreactive solution4 +Concentration, and then assess catalysis
The fixed nitrogen performance of agent.Test result shows the photocatalysis fixed nitrogen performance that this sample has and case 4 is equally outstanding.
Embodiment 6:
A kind of preparation method of rose-shaped photocatalysis fixed nitrogen catalyst BiOCl, includes the following steps:
(1) glucose for weighing 6g is placed in the deionized water of 60ml, and it is water-soluble that uniform glucose is obtained after magnetic agitation
Liquid；
(2) glucose solution of step (1) is transferred in the reaction kettle of 100ml, 180 DEG C at a temperature of into
Row hydro-thermal reaction 12h, then the product of hydro-thermal reaction is used into deionized water and ethanol washing respectively, in 6000 turns/min, centrifugation
Between be centrifuged under conditions of 5min 4 times, then dried for 24 hours in 60 DEG C of temperature, obtain carbonaceous mesophase spherules；
(3) it the carbonaceous mesophase spherules obtained in step (2) is weighed into 0.3g is placed in and fill 120ml and concentration is
In the acetic acid aqueous solution of 1mol/L, then magnetic agitation keeps its evenly dispersed；
(4) Bi (NO of 0.01mol is added into step (3) obtained solution3)3·5H2O, until adding again after being completely dissolved
Enter the NH of 0.01mol4Tan precipitate is obtained after Cl, magnetic agitation 12h and standing；
(5) tan precipitate obtained in step (4) is dried to 12h under the conditions of 80 DEG C, and with temperature for 500
DEG C, heating rate is 1 DEG C/min, and soaking time is that 2h is catalyzed drying precipitate and calcining to get to rose-shaped BiOCl
Agent.
Photocatalysis fixed nitrogen performance test to above-mentioned BiOCl catalyst: rose-shaped BiOCl catalyst obtained by 5mg is taken to put
Enter into the hydrochloric acid reaction tube for the 60ml for filling 0.1mol/L concentration simultaneously ultrasonic disperse, is continually fed into confined reaction system
N2.By reaction tube under the conditions of being protected from light magnetic agitation 30min, make catalyst surface to dilute hydrochloric acid and N2It is flat to reach adsorption-desorption
Weighing apparatus.3h is irradiated using xenon lamp as light source, takes the reaction solution of 2ml to be centrifuged every l h among it.It is molten that a certain amount of ion chromatography is added
Liquid is based on Beer law, utilizes the NH in ultraviolet-visible spectrophotometer test photoreactive solution4 +Concentration, and then assess catalysis
The fixed nitrogen performance of agent.Test result shows the photocatalysis fixed nitrogen performance that this sample has and embodiment 4 is equally outstanding.
From the XRD diagram of Fig. 5 as can be seen that pre-prepared sample at 12 °, 24.2 °, 25.9 °, 32.6 °, 33.5 °,
Diffraction maximum at 34.8 °, 36.6 °, 40.1 °, 46.7 °, 48.3 °, 49.9 °, 53.3 °, 54.1 °, 55.2 ° and 58.6 ° is right respectively
It answers (001) of BiOBr standard card (JCPDS No.09-0393), (002) (101), (110), (102), (111), (033),
(112), (200), (201), (113), (202), (211) (1,04) and (212) crystal face spread out without discovery impurity peaks in map
It is sharp to penetrate peak, relative intensity is big, thus infers that sample is pure BiOCl and good crystallinity.In addition, can from the SEM figure of Fig. 5
The BiOCl catalyst prepared out is formed by BiOCl nano flake self assembly, be rosettes structure and pattern it is single.It is this
Rosettes structure made of self assembly cannot can be improved light utilization efficiency, and be conducive to light induced electron and hole transfer, drop
Low light induced electron and hole-recombination, and then improve its catalytic performance.In addition, the catalyst is after ultrasonic vibration for 24 hours, pattern does not have
Any variation shows there is very strong structural stability, has good recycling effect；It is for example attached that experimental result is recycled
Shown in Fig. 8.It can be obtained by analyzing above, by rose-shaped BiOCl fixed nitrogen catalyst made from the invention preparation method, not only be reacted
Mild condition, preparation cost is low, and sample surface morphology is uniform, and photocatalysis fixed nitrogen is had excellent performance.
The halogeno salt that embodiment 7 to embodiment 9 is selected is NH4Br, and the photochemical catalyst ingredient being prepared is BiOCl.
Embodiment 7:
A kind of preparation method of rose-shaped photocatalysis fixed nitrogen catalyst BiOCl, includes the following steps:
(1) glucose for weighing 5g is placed in the deionized water of 60ml, and it is water-soluble that uniform glucose is obtained after magnetic agitation
Liquid；
(2) glucose solution of step (1) is transferred in the reaction kettle of 100ml, 180 DEG C at a temperature of into
Row hydro-thermal reaction 12h, then the product of hydro-thermal reaction is used into deionized water and ethanol washing respectively, in 6000 turns/min, centrifugation
Between be centrifuged under conditions of 5min 4 times, then dried for 24 hours in 60 DEG C of temperature, obtain carbonaceous mesophase spherules；
(3) by the carbonaceous mesophase spherules obtained in step (2) weigh 0.5g be placed in fill 200ml, concentration is
In the acetic acid aqueous solution beaker of 1.5mol/L, then magnetic agitation keeps its evenly dispersed；
(4) Bi (NO of 0.02mol is added into step (3) obtained solution3)3·5H2O, until adding again after being completely dissolved
Enter the NH of 0.02mol4Tan precipitate is obtained after Br, magnetic agitation 12h and standing；
(5) tan precipitate obtained in step (4) is dried to 12h under the conditions of 80 DEG C, and with temperature for 500
DEG C, heating rate is 2 DEG C/min, and soaking time arrives three-dimensional hollow BiOBr photocatalysis with calcining to drying precipitate for 2h
Fixed nitrogen catalyst.
Photocatalysis fixed nitrogen performance test to above-mentioned BiOBr catalyst: three-dimensional hollow BiOBr catalyst obtained by 5mg is taken to put
Enter to filling in 0.00005mol dilute hydrochloric acid reaction tube and ultrasonic disperse, is continually fed into N in confined reaction system2.It will reaction
Pipe magnetic agitation 30min under the conditions of being protected from light makes catalyst surface to dilute hydrochloric acid and N2Reach adsorption-desorption balance.With xenon lamp
3h is irradiated as light source, takes the reaction solution of 2ml to be centrifuged every l h among it.A certain amount of ion chromatography solution is added, is based on Bill
Law utilizes the NH in ultraviolet-visible spectrophotometer test photoreactive solution4 +Concentration, and then assess the fixed nitrogen of catalyst
Energy.The photocatalysis fixed nitrogen performance of this sample is as is illustrated by figs. 11 and 12.
Embodiment 8:
A kind of preparation method of rose-shaped photocatalysis fixed nitrogen catalyst BiOCl, includes the following steps:
(1) glucose for weighing 3g is placed in the deionized water of 30ml, and it is water-soluble that uniform glucose is obtained after magnetic agitation
Liquid；
(2) glucose solution of step (1) is transferred in the reaction kettle of 50ml, 180 DEG C at a temperature of into
Row hydro-thermal reaction 12h, then the product of hydro-thermal reaction is used into deionized water and ethanol washing respectively, in 6000 turns/min, centrifugation
Between be centrifuged under conditions of 5min 4 times, then dried for 24 hours in 60 DEG C of temperature, obtain carbonaceous mesophase spherules；
(3) by the carbonaceous mesophase spherules obtained in step (2) weigh 0.4g be placed in fill 120ml, concentration is
In the acetic acid aqueous solution beaker of 1.2mol/L, then magnetic agitation keeps its evenly dispersed；
(4) Bi (NO of 0.015mol is added into step (3) obtained solution3)3·5H2O, until after being completely dissolved again
The NH of 0.015ml is added4Tan precipitate is obtained after Br, magnetic agitation 12h and standing；
(5) tan precipitate obtained in step (4) is dried to 12h under the conditions of 80 DEG C, and with temperature for 500
DEG C, heating rate is 2 DEG C/min, and soaking time arrives three-dimensional hollow BiOBr photocatalysis with calcining to drying precipitate for 2h
Fixed nitrogen catalyst.
Photocatalysis fixed nitrogen performance test to above-mentioned BiOBr catalyst: three-dimensional hollow BiOBr catalyst obtained by 5mg is taken to put
Enter to filling in 0.00005mol dilute hydrochloric acid reaction tube and ultrasonic disperse, is continually fed into N in confined reaction system2.It will reaction
Pipe magnetic agitation 30min under the conditions of being protected from light makes catalyst surface to dilute hydrochloric acid and N2Reach adsorption-desorption balance.With xenon lamp
3h is irradiated as light source, takes the reaction solution of 2ml to be centrifuged every l h among it.A certain amount of ion chromatography solution is added, is based on Bill
Law utilizes the NH in ultraviolet-visible spectrophotometer test photoreactive solution4 +Concentration, and then assess the fixed nitrogen of catalyst
Energy.Test result shows the photocatalysis fixed nitrogen performance that this sample has and embodiment 7 is equally outstanding.
Embodiment 9:
A kind of preparation method of rose-shaped photocatalysis fixed nitrogen catalyst BiOCl, includes the following steps:
(1) glucose for weighing 6g is placed in the deionized water of 60ml, and it is water-soluble that uniform glucose is obtained after magnetic agitation
Liquid；
(2) glucose solution of step (1) is transferred in the reaction kettle of 100ml, 180 DEG C at a temperature of into
Row hydro-thermal reaction 12h, then the product of hydro-thermal reaction is used into deionized water and ethanol washing respectively, in 6000 turns/min, centrifugation
Between be centrifuged under conditions of 5min 4 times, then dried for 24 hours in 60 DEG C of temperature, obtain carbonaceous mesophase spherules；
(3) it the carbonaceous mesophase spherules obtained in step (2) is weighed into 0.3g is placed in and fill 120ml and concentration is
In the acetic acid aqueous solution of 1mol/L, then magnetic agitation keeps its evenly dispersed；
(4) Bi (NO of 0.01mol is added into step (3) obtained solution3)3·5H2O, until adding again after being completely dissolved
Enter the NH of 0.01mol4Tan precipitate is obtained after Br, magnetic agitation 12h and standing；
(5) tan precipitate obtained in step (4) is dried to 12h under the conditions of 80 DEG C, and with temperature for 500
DEG C, heating rate is 1 DEG C/min, and soaking time arrives three-dimensional hollow BiOBr photocatalysis with calcining to drying precipitate for 2h
Fixed nitrogen catalyst.
Photocatalysis fixed nitrogen performance test to above-mentioned BiOBr catalyst: three-dimensional hollow BiOBr catalyst obtained by 5mg is taken to put
Enter to filling in 0.00005mol dilute hydrochloric acid reaction tube and ultrasonic disperse, is continually fed into N in confined reaction system2.It will reaction
Pipe magnetic agitation 30min under the conditions of being protected from light makes catalyst surface to dilute hydrochloric acid and N2Reach adsorption-desorption balance.With xenon lamp
3h is irradiated as light source, takes the reaction solution of 2ml to be centrifuged every l h among it.A certain amount of ion chromatography solution is added, is based on Bill
Law utilizes the NH in ultraviolet-visible spectrophotometer test photoreactive solution4 +Concentration, and then assess the fixed nitrogen of catalyst
Energy.Test result shows the photocatalysis fixed nitrogen performance that this sample has and embodiment 7 is equally outstanding.
From the XRD diagram of Fig. 9 as can be seen that pre-prepared sample at 10.8 °, 21.7 °, 25.2 °, 31.7 °, 32.2 °,
Diffraction maximum at 34.1 °, 39.2 °, 46.2 °, 50.5 °, 53.3 ° and 57.1 ° respectively corresponds BiOBr standard card (JCPDS
No.09-0393 (001)), (002) (011), (102), (110), (111) (112), (200), (104), (211) and (212)
Crystal face, without discovery impurity peaks in map, diffraction maximum is sharp, and relative intensity is big, thus infers that sample is pure BiOBr and crystallinity
It is good.In addition, as can be seen that the catalyst of preparation is three-dimensional hollow flower-like structure and pattern is uniform from the SEM figure of Figure 10.It is
It is formed by BiOBr nano flake self assembly.Three-dimensional hollow flower-like structure is conducive to it to nitrogen adsorption；And then improve its catalytic
Energy；In addition, the catalyst, after ultrasonic vibration for 24 hours, pattern does not have any variation, shows that there is very strong structural stability, make
It is as shown in Fig. 12 that experimental result is recycled with good recycling effect in it.It can be obtained by analyzing above, by this hair
Three-dimensional hollow BiOBr fixed nitrogen catalyst made from bright preparation method, not only reaction condition is mild, and preparation cost is low, sample surfaces
Pattern is uniform, and photocatalysis fixed nitrogen is had excellent performance.
Claims (8)
1. a kind of preparation method of the BiOX fixed nitrogen photochemical catalyst of three-dimensional structure, which comprises the steps of:
(1) it weighs a certain amount of glucose to be placed in deionized water, uniform glucose solution is obtained after magnetic agitation；
(2) glucose solution of step (1) is transferred in reaction kettle, carries out hydro-thermal reaction, then by hydro-thermal reaction
Product uses deionized water and ethanol washing respectively, is centrifuged and dries, obtains carbonaceous mesophase spherules；
(3) carbonaceous mesophase spherules obtained in step (2) are placed in acetic acid aqueous solution, magnetic agitation divides it uniformly
It dissipates；
(4) Bi (NO is added into step (3) obtained solution3)3·5H2O, until adding same molar after being completely dissolved
Halogeno salt, magnetic agitation and stand after obtain tan precipitate；
(5) all different oxyhalogen of ingredient and pattern is obtained after the tan precipitate obtained in step (4) is dry, calcining
Change bismuth photochemical catalyst.
2. a kind of preparation method of the BiOX fixed nitrogen photochemical catalyst of three-dimensional structure according to claim 1, feature
It is, the halogeno salt in step (4) is selected from KI, NH4Cl、NH4One of Br.
3. a kind of preparation method of the BiOX fixed nitrogen photochemical catalyst of three-dimensional structure according to claim 1, feature
It is, glucose and the mass ratio of deionized water are between 1:8~1:12 range in step (1).
4. a kind of preparation method of the BiOX fixed nitrogen photochemical catalyst of three-dimensional structure according to claim 1, feature
It is, the condition of hydro-thermal reaction in step (2) are as follows: 60ml glucose solution is put into 100ml reaction kettle, temperature 160~200
DEG C, 10~16h of soaking time.
5. a kind of preparation method of the BiOX fixed nitrogen photochemical catalyst of three-dimensional structure according to claim 1, feature
It is, the centrifugal condition in step (2) are as follows: centrifugal rotational speed is 6000 turns/min, centrifugation time 5min, washs and be centrifuged number
It is 4 times.
6. a kind of preparation method of the BiOX fixed nitrogen photochemical catalyst of three-dimensional structure according to claim 1, feature
It is, the drying condition in step (2) are as follows: drying temperature is 60 DEG C, and drying time is for 24 hours.
7. a kind of preparation method of the BiOX fixed nitrogen photochemical catalyst of three-dimensional structure according to claim 2, feature
It is, the amount of carbonaceous mesophase spherules used in step (3) is 0.3~0.5g, and the concentration of acetic acid is 1~2mol/L aqueous solution,
BiNO3·5H2The amount of O is 0.01mol, KI, the NH used4Cl or NH4The amount of Br be 0.01mol, 80~120 DEG C of drying temperature.
8. a kind of preparation method of the BiOX fixed nitrogen photochemical catalyst of three-dimensional structure according to claim 1, feature
It is, the condition calcined in step (5) are as follows: 500 DEG C of temperature, 1~2 DEG C/min of heating rate, soaking time is 2~3h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560174A (en) * | 2019-08-16 | 2019-12-13 | 南京理工大学 | BiOI/C/PANI heterojunction material and preparation method thereof |
| CN112391651A (en) * | 2020-09-18 | 2021-02-23 | 厦门大学 | BiOBr/TiO containing oxygen vacancies2Nanotube array composite electrode, preparation method thereof and application of nanotube array composite electrode in photoelectrocatalysis nitrogen fixation |
| CN113213508A (en) * | 2021-04-27 | 2021-08-06 | 金华市浙工大创新联合研究院 | Method for synthesizing ammonia through photocatalysis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179435A (en) * | 2016-07-04 | 2016-12-07 | 浙江工商大学 | Visible light catalyst C@Bi2o3biOBr BiOI and preparation thereof and the application in sterilization |
| CN109289881A (en) * | 2018-11-21 | 2019-02-01 | 大连工业大学 | A kind of preparation and solar energy fixed nitrogen application of carbon nano-fiber support BiOX photocatalyst |
-
2019
- 2019-03-14 CN CN201910192231.XA patent/CN109894126A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179435A (en) * | 2016-07-04 | 2016-12-07 | 浙江工商大学 | Visible light catalyst C@Bi2o3biOBr BiOI and preparation thereof and the application in sterilization |
| CN109289881A (en) * | 2018-11-21 | 2019-02-01 | 大连工业大学 | A kind of preparation and solar energy fixed nitrogen application of carbon nano-fiber support BiOX photocatalyst |
Non-Patent Citations (2)
| Title |
|---|
| BAI JIN等: "Influence of Solvothermal Post-Treatment on Photochemical Nitrogen Conversion to Ammonia with g-C3N4 Catalyst", 《ACTA PHYS. -CHIM. SIN.》 * |
| 李中华: "可见光性能增强的卤氧化铋光催化研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560174A (en) * | 2019-08-16 | 2019-12-13 | 南京理工大学 | BiOI/C/PANI heterojunction material and preparation method thereof |
| CN110560174B (en) * | 2019-08-16 | 2022-06-28 | 南京理工大学 | BiOI/C/PANI heterojunction material and preparation method thereof |
| CN112391651A (en) * | 2020-09-18 | 2021-02-23 | 厦门大学 | BiOBr/TiO containing oxygen vacancies2Nanotube array composite electrode, preparation method thereof and application of nanotube array composite electrode in photoelectrocatalysis nitrogen fixation |
| CN112391651B (en) * | 2020-09-18 | 2021-10-26 | 厦门大学 | BiOBr/TiO containing oxygen vacancies2Nanotube array composite electrode, preparation method thereof and application of nanotube array composite electrode in photoelectrocatalysis nitrogen fixation |
| CN113213508A (en) * | 2021-04-27 | 2021-08-06 | 金华市浙工大创新联合研究院 | Method for synthesizing ammonia through photocatalysis |
| CN113213508B (en) * | 2021-04-27 | 2022-08-12 | 金华市浙工大创新联合研究院 | Method for synthesizing ammonia through photocatalysis |
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