CN104971756A - Supported Bi2O2CO3-BiPO4 composite photocatalyst and preparation method thereof - Google Patents

Supported Bi2O2CO3-BiPO4 composite photocatalyst and preparation method thereof Download PDF

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CN104971756A
CN104971756A CN201510296331.9A CN201510296331A CN104971756A CN 104971756 A CN104971756 A CN 104971756A CN 201510296331 A CN201510296331 A CN 201510296331A CN 104971756 A CN104971756 A CN 104971756A
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bipo
mixed solution
catalyst
preparation
support type
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刘玉民
光景
吕华
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Henan Normal University
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Henan Normal University
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Abstract

The invention discloses a supported Bi2O2CO3-BiPO4 composite photocatalyst and a preparation method thereof, belonging to the technical field of inorganic environment-friendly photocatalytic materials. The Key point of the technical scheme disclosed in the invention is as follows: the Bi2O2CO3-BiPO4 composite photocatalyst is composited with Ni0.4Zn0.6Fe2O4 carrier particles with soft magnetism. The invention also discloses the preparation method of the supported Bi2O2CO3-BiPO4 composite photocatalyst. The supported Bi2O2CO3-BiPO4 composite photocatalyst disclosed in the invention has high photocatalytic activity and is easy to isolate, recover and recycle. The preparation process is simple in operation, is easy to control and low in cost.

Description

A kind of support type Bi 2o 2cO 3-BiPO 4composite photo-catalyst and preparation method thereof
Technical field
The invention belongs to inorganic environment-friendly catalysis material technical field, be specifically related to a kind of support type Bi 2o 2cO 3-BiPO 4composite photo-catalyst and preparation method thereof.
Background technology
In recent decades, along with aggravation and the energy shortage of environmental pollution, solar energy photocatalytic degradation of organic substances is utilized to become the important means solving environmental pollution and energy shortage problem.But traditional photochemical catalyst is (as TiO 2, ZnO etc.) there is photohole in actual use and the shortcoming such as electron recombination rate is high, quantum efficiency is low and photocatalytic activity is on the low side, limit the further application of photocatalysis technology at environment and energy field.Therefore, the catalyst that design has a high light catalytic activity becomes one of great research topic that photocatalysis science and Environmental capacity face.For solving this difficult problem, usually there are two kinds of thinkings: one is as doping, compound etc. to the modification of traditional photochemical catalyst; Two is development of new photochemical catalysts.
Bi 2o 2cO 3it is a kind of novel catalysis material, its energy gap is 3.4eV, when the illumination being subject to energy and being not less than its band gap is penetrated, can produce conduction band electron and valence band hole, there is stronger reproducibility and oxidisability, directly organic pollutant degradation can be become nontoxic water and carbon dioxide.But Bi 2o 2cO 3the recombination rate in optical excitation generation electronics and hole is higher, photo-quantum efficiency is low, can not meet the needs of commercial Application.Semiconductors coupling improves Bi 2o 2cO 3the effective means of photocatalysis performance, according to the difference of different semiconductor conduction band and valence-band level, makes photo-generated carrier be effectively separated, and reduces the recombination probability of carrier, improves quantum efficiency, and then improves its photocatalytic activity.BiPO 4be another important catalysis material in bismuth system oxide, energy gap is 3.85eV, and the crystal structure of its uniqueness and electronic structure make it have wider absorption band gap and higher photocatalytic activity.Research shows, Bi 2o 2cO 3the conduction band potential E of photochemical catalyst cB=0.16eV, valence band electromotive force E vB=3.56eV, and BiPO 4the conduction band potential E of photochemical catalyst cB=0.43eV, valence band electromotive force E vB=4.28eV.At Bi 2o 2cO 3-BiPO 4in composite semiconductor, Bi 2o 2cO 3conduction band potential more negative, light induced electron is easily from the Bi that energy level is low 2o 2cO 3conduction band moves to the high BiPO of energy level 4on conduction band; Meanwhile, BiPO 4valence band electromotive force corrigendum, photohole is easily from the BiPO that energy level is high 4valence band moves to the low Bi of energy level 2o 2cO 3in valence band, thus improve the separative efficiency of photogenerated charge, and then improve its photocatalytic activity.
Although Bi 2o 2cO 3-BiPO 4composite photocatalyst has higher quantum efficiency and catalytic activity, but due to its particle diameter less, itself there is easily cohesion, easy in inactivation, difficult sedimentation and reclaim the shortcomings such as difficult, making its application in wastewater treatment have certain limitation.Therefore, time in actual application as wastewater treatment, must by Bi 2o 2cO 3-BiPO 4composite photocatalyst is carried on certain carrier and could uses.In recent years, a kind of efficient, quick, economic magnetic separation technique is widely used in the fields such as environmental protection.If by a kind of magnetic component load at Bi 2o 2cO 3-BiPO 4composite photocatalyst surface, not only can avoid the reunion between photocatalyst granular, improve its photocatalytic activity, can also increase Bi 2o 2cO 3-BiPO 4the rate of settling of composite photocatalyst, and utilize magnetic separation technique to be gone out by its quick separating from wastewater treatment system, solve photocatalysis technology key issue in actual applications.
Summary of the invention
It is high and be easy to separation and recovery and reusable support type Bi that the technical problem that the present invention solves there is provided a kind of photocatalytic activity 2o 2cO 3-BiPO 4composite photo-catalyst.
Another technical problem that the present invention solves there is provided a kind of simple to operate, be easy to control and support type Bi with low cost 2o 2cO 3-BiPO 4the preparation method of composite photo-catalyst.
The present invention adopts following technical scheme, a kind of support type Bi for solving the problems of the technologies described above 2o 2cO 3-BiPO 4composite photo-catalyst, it is characterized in that by by Bi 2o 2cO 3-BiPO 4composite photocatalyst and carrier granular soft magnetism Ni 0.4zn 0.6fe 2o 4compound is formed, wherein soft magnetism Ni 0.4zn 0.6fe 2o 4with Bi 2o 2cO 3-BiPO 4the mass ratio of composite photocatalyst is 0.1-0.3:1, Bi 2o 2cO 3-BiPO 4[PO in composite photocatalyst 4 3-] and [Bi 3+] mol ratio be 0.05:1.
Support type Bi of the present invention 2o 2cO 3-BiPO 4the preparation method of composite photo-catalyst, it is characterized in that comprising the following steps: the ratio of nickel nitrate, zinc nitrate and ferric nitrate 0.2:0.3:1 in molar ratio mixes with deionized water and obtains mixed solution by (1), disodium ethylene diamine tetraacetate (EDTA) is added again in mixed solution, wherein the addition of EDTA and the mol ratio of nickel nitrate are 4:1, in the water-bath of 80 DEG C, kept by the mixed system of gained 12h to obtain wet gel, wet gel obtains xerogel through 110 DEG C of dryings, then xerogel is obtained soft magnetism Ni at 400-600 DEG C of calcining 1h 0.4zn 0.6fe 2o 4; (2) ratio of two hypophosphite monohydrate sodium dihydrogens, five water bismuth nitrates and urea 0.05:1:3 is in molar ratio mixed with deionized water obtain mixed solution under agitation, in mixed solution, add ammoniacal liquor regulates the pH value of mixed solution to be 4, adds soft magnetism Ni 0.4zn 0.6fe 2o 4then be transferred in hydrothermal reaction kettle after mixed system being continued under the condition of room temperature to stir 2h, then hydrothermal reaction kettle is put into microwave dissolver in 180-200 DEG C of microwave reaction 10-30min, after cooling, filtration, washing, drying, obtain the support type Ni with high catalytic activity 0.4zn 0.6fe 2o 4/ Bi 2o 2cO 3-BiPO 4composite photo-catalyst.
Further restriction, in the mixed solution of step (1), the molar concentration of nickel nitrate is 0.05-0.1mol/L.
Further restriction, in the mixed solution of step (2), the molar concentration of bismuth nitrate is 0.05-0.1mol/L.
Further restriction, step adds soft magnetism Ni in (2) 0.4zn 0.6fe 2o 4amount be Bi 2o 2cO 3-BiPO 4the 0.1-0.3 of compound photocatalysis quality doubly.
Support type Ni of the present invention 0.4zn 0.6fe 2o 4/ Bi 2o 2cO 3-BiPO 4the photocatalytic activity of composite photo-catalyst is high and be easy to separation and recovery and repeat to recycle, and preparation process is simple to operate, be easy to control and with low cost.
Detailed description of the invention
Further describe the present invention below in conjunction with embodiment, it is noted that the present invention is not limited to following each embodiment.
Embodiment 1
(1) under agitation, amount of substance is respectively 0.88 × 10 -3mol, 1.32 × 10 -3mol and 4.4 × 10 -3the nickel nitrate of mol, zinc nitrate and ferric nitrate deionized water are made into mixed solution, and in mixed solution, the molar concentration of bismuth nitrate is 0.05mol/L, then in mixed solution, adds 3.52 × 10 -3the EDTA of mol, in the water-bath of 80 DEG C, kept by the mixed system of gained 12h to obtain wet gel, wet gel obtains xerogel through 110 DEG C of dryings, then xerogel is obtained soft magnetism Ni in 600 DEG C of calcining 1h 0.4zn 0.6fe 2o 4;
(2) under agitation amount of substance is respectively 1.0 × 10 -3the two hypophosphite monohydrate sodium dihydrogens of mol, 0.02mol and 0.06mol, five water bismuth nitrates and urea deionized water are made into mixed solution, in mixed solution, the molar concentration of bismuth nitrate is 0.05mol/L, in mixed solution, add ammoniacal liquor regulates the pH value of mixed solution to be 4, then adds the soft magnetism Ni that 0.525g step (1) is obtained 0.4zn 0.6fe 2o 4be transferred in hydrothermal reaction kettle after mixed system being continued under the condition of room temperature stir 2h, then hydrothermal reaction kettle is put into microwave dissolver in 180 DEG C of microwave reaction 30min, after cooling, filtration, washing, drying, obtain the support type Ni with high catalytic activity 0.4zn 0.6fe 2o 4/ Bi 2o 2cO 3-BiPO 4composite photo-catalyst.
Embodiment 2
(1) under agitation, amount of substance is respectively 1.76 × 10 -3mol, 2.64 × 10 -3mol and 8.8 × 10 -3the nickel nitrate of mol, zinc nitrate and ferric nitrate deionized water are made into mixed solution, and in mixed solution, the molar concentration of bismuth nitrate is 0.08mol/L, then in mixed solution, adds 7.04 × 10 -3the EDTA of mol, in the water-bath of 80 DEG C, kept by the mixed system of gained 12h to obtain wet gel, wet gel obtains xerogel through 110 DEG C of dryings, then xerogel is obtained soft magnetism Ni at 400 DEG C of calcining 1h 0.4zn 0.6fe 2o 4;
(2) under agitation amount of substance is respectively 1.0 × 10 -3the two hypophosphite monohydrate sodium dihydrogens of mol, 0.02mol and 0.06mol, five water bismuth nitrates and urea deionized water are made into mixed solution, in mixed solution, the molar concentration of bismuth nitrate is 0.08mol/L, in mixed solution, add ammoniacal liquor regulates the pH value of mixed solution to be 4, then adds the soft magnetism Ni that 1.05g step (1) is obtained 0.4zn 0.6fe 2o 4be transferred in hydrothermal reaction kettle after mixed system being continued under the condition of room temperature stir 2h, then hydrothermal reaction kettle is put into microwave dissolver in 180 DEG C of microwave reaction 20min, after cooling, filtration, washing, drying, obtain the support type Ni with high catalytic activity 0.4zn 0.6fe 2o 4/ Bi 2o 2cO 3-BiPO 4composite photo-catalyst.
Embodiment 3
(1) under agitation, amount of substance is respectively 2.64 × 10 -3mol, 3.96 × 10 -3mol and 13.2 × 10 -3the nickel nitrate of mol, zinc nitrate and ferric nitrate deionized water are made into mixed solution, and in mixed solution, the molar concentration of bismuth nitrate is 0.1mol/L, then in mixed solution, adds 10.56 × 10 -3the EDTA of mol, in the water-bath of 80 DEG C, kept by the mixed system of gained 12h to obtain wet gel, wet gel obtains xerogel through 110 DEG C of dryings, then xerogel is obtained soft magnetism Ni in 500 DEG C of calcining 1h 0.4zn 0.6fe 2o 4;
(2) under agitation amount of substance is respectively 1.0 × 10 -3the two hypophosphite monohydrate sodium dihydrogens of mol, 0.02mol and 0.06mol, five water bismuth nitrates and urea deionized water are made into mixed solution, in mixed solution, the molar concentration of bismuth nitrate is 0.1mol/L, in mixed solution, add ammoniacal liquor regulates the pH value of mixed solution to be 4, then adds the soft magnetism Ni that 1.575g step (2) is obtained 0.4zn 0.6fe 2o 4be transferred in hydrothermal reaction kettle after mixed solution being continued under the condition of room temperature stir 2h, then hydrothermal reaction kettle is put into microwave dissolver in 200 DEG C of microwave reaction 10min, after cooling, filtration, washing, drying, obtain the support type Ni with high catalytic activity 0.4zn 0.6fe 2o 4/ Bi 2o 2cO 3-BiPO 4composite photo-catalyst.
Embodiment above describes general principle of the present invention, principal character and advantage; the technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and description just illustrates principle of the present invention; under the scope not departing from the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.

Claims (5)

1. a support type Bi 2o 2cO 3-BiPO 4composite photo-catalyst, it is characterized in that by by Bi 2o 2cO 3-BiPO 4composite photocatalyst and carrier granular soft magnetism Ni 0.4zn 0.6fe 2o 4compound is formed, wherein soft magnetism Ni 0.4zn 0.6fe 2o 4with Bi 2o 2cO 3-BiPO 4the mass ratio of composite photocatalyst is 0.1-0.3:1, Bi 2o 2cO 3-BiPO 4[PO in composite photocatalyst 4 3-] and [Bi 3+] mol ratio be 0.05:1.
2. a support type Bi according to claim 1 2o 2cO 3-BiPO 4the preparation method of composite photo-catalyst, it is characterized in that comprising the following steps: the ratio of nickel nitrate, zinc nitrate and ferric nitrate 0.2:0.3:1 in molar ratio mixes with deionized water and obtains mixed solution by (1), EDTA is added again in mixed solution, wherein the addition of EDTA and the mol ratio of nickel nitrate are 4:1, in the water-bath of 80 DEG C, kept by the mixed system of gained 12h to obtain wet gel, wet gel obtains xerogel through 110 DEG C of dryings, then xerogel is obtained soft magnetism Ni at 400-600 DEG C of calcining 1h 0.4zn 0.6fe 2o 4; (2) ratio of two hypophosphite monohydrate sodium dihydrogens, five water bismuth nitrates and urea 0.05:1:3 is in molar ratio mixed with deionized water obtain mixed solution under agitation, in mixed solution, add ammoniacal liquor regulates the pH value of mixed solution to be 4, adds soft magnetism Ni 0.4zn 0.6fe 2o 4then be transferred in hydrothermal reaction kettle after mixed system being continued under the condition of room temperature to stir 2h, then hydrothermal reaction kettle is put into microwave dissolver in 180-200 DEG C of microwave reaction 10-30min, after cooling, filtration, washing, drying, obtain the support type Ni with high catalytic activity 0.4zn 0.6fe 2o 4/ Bi 2o 2cO 3-BiPO 4composite photo-catalyst.
3. support type Bi according to claim 2 2o 2cO 3-BiPO 4the preparation method of composite photo-catalyst, is characterized in that: in the mixed solution of step (1), the molar concentration of nickel nitrate is 0.05-0.1mol/L.
4. support type Bi according to claim 2 2o 2cO 3-BiPO 4the preparation method of composite photo-catalyst, is characterized in that: in the mixed solution of step (2), the molar concentration of bismuth nitrate is 0.05-0.1mol/L.
5. support type Bi according to claim 2 2o 2cO 3-BiPO 4the preparation method of composite photo-catalyst, is characterized in that: step adds soft magnetism Ni in (2) 0.4zn 0.6fe 2o 4amount be Bi 2o 2cO 3-BiPO 4the 0.1-0.3 of compound photocatalysis quality doubly.
CN201510296331.9A 2015-06-03 2015-06-03 Supported Bi2O2CO3-BiPO4 composite photocatalyst and preparation method thereof Pending CN104971756A (en)

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Publication number Priority date Publication date Assignee Title
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