CN106964334A - A kind of full spectral response type catalyst material and its production and use - Google Patents
A kind of full spectral response type catalyst material and its production and use Download PDFInfo
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- CN106964334A CN106964334A CN201710312308.3A CN201710312308A CN106964334A CN 106964334 A CN106964334 A CN 106964334A CN 201710312308 A CN201710312308 A CN 201710312308A CN 106964334 A CN106964334 A CN 106964334A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 239000000463 material Substances 0.000 title claims abstract description 97
- 230000004044 response Effects 0.000 title claims abstract description 66
- 230000003595 spectral effect Effects 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 37
- 238000000137 annealing Methods 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 150000001621 bismuth Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000012805 post-processing Methods 0.000 claims abstract description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 56
- 230000015556 catabolic process Effects 0.000 claims description 20
- 238000006731 degradation reaction Methods 0.000 claims description 20
- 229910052797 bismuth Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000356 contaminant Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 5
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 230000009514 concussion Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 29
- 229940012189 methyl orange Drugs 0.000 description 29
- 230000003197 catalytic effect Effects 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011941 photocatalyst Substances 0.000 description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 8
- 230000005855 radiation Effects 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 description 4
- WKLWZEWIYUTZNJ-UHFFFAOYSA-K diacetyloxybismuthanyl acetate Chemical class [Bi+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WKLWZEWIYUTZNJ-UHFFFAOYSA-K 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910002115 bismuth titanate Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 bismuth oxide compound Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- NAYQZIDUTPGBPA-UHFFFAOYSA-N dimethylbismuth Chemical class C[Bi]C NAYQZIDUTPGBPA-UHFFFAOYSA-N 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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 provides a kind of full spectral response type catalyst material and its production and use, the preparation method of the catalyst material comprises the following steps：(1) bismuth salt is dissolved in reduction solvent, graphene oxide solution is added after being well mixed, stirring obtains mixed solution；(2) the mixed solution heating obtained step (1) is reacted, and compound is obtained through post processing after reaction；(3) compound for obtaining step (2) is made annealing treatment under protective atmosphere, obtains full spectral response type catalyst material.The present invention urges the structure and composition of agent by rationally designing light, has widened the application conditions of photochemical catalyst, obtained photochemical catalyst is all had higher photocatalytic degradation efficiency in ultraviolet, visible and infrared band.
Description
Technical field
The invention belongs to environmentally conscious materials field, it is related to a kind of full spectral response type catalyst material and preparation method thereof and use
On the way, it is more particularly to a kind of based on graphene nanocomposite material, all possess under ultraviolet light, visible ray and Infrared irradiation
The photocatalytic nanometer powder of the ability of efficient degradation pollutant.
Background technology
Photocatalyst can make full use of the honest and sunshine of " green " come effectively degrade it is various it is inorganic with have
Organic pollutants, be solve one of global environmental degradation at present and energy level crisis it is important by way of.Photocatalytic degradation is used as one
The method for planting new processing pollutant, with advantages below：(1) permineralization pollutant, nontoxic (such as CO of final product2With
H2O)；(2) it can carry out at room temperature and atmospheric pressure；(3) low energy consumption；(4) economic green.Therefore, from Fujishima in 1972 and
Since Honda has found the photoelectrocatalysis decomposition of water on n-type semi-conducting electrode, the semi-conducting material based on oxide is special
It is not titanium dioxide, gets more and more people's extensive concerning.
The energy gap of conventional semiconductor material is larger, corresponding excitation wavelength ultra-violet (UV) band and portion of energy it is higher can
Jian Guang areas.However, in the solar radiation energy of earth's surface is actually reached, ultraviolet component is less than 5%, it is seen that composition about 45%,
Infrared composition about 50%, therefore this photocatalysis feature of conventional semiconductor material seriously limits it under the conditions of solar source
Photocatalytic pollutant degradation efficiency, also have influence on it and lack application under the conditions of ultraviolet source indoors.From utilizing solar energy
Angle set out, most economical photochemical catalyst should be can simultaneously utilize sunshine in ultraviolet light, visible ray and infrared light, and
And with good stability.In addition, the optoacoustic electron-hole of conventional semiconductor material is easily combined, cause photo-quantum efficiency
Reduction, significantly limit the efficiency of its degradation of contaminant.
Therefore, the infrared full spectroscopy catalytic agent degradable organic pollutant of the efficient UV, visible light of development of new turns into energy-saving ring
One of crucial Science and Technology problem in guarantor field.
The most important condition of photochemical catalyst is can to produce electron-hole pair, and can pass through the effective ground resistance of electron transfer mediator
Only electronics and the quick of hole are combined.Graphene and its derivative graphene oxide have preferable electric conductivity and mechanicalness because of it
There is great application prospect in photocatalysis field as electron transmission bridge.Development can produce partly leading for electron-hole pair
The nano composite structure of body and the graphene that can transmit electronics, is that sunshine directly utilizes the important need with catalytic field.
The A of CN 104353449 disclose a kind of preparation method of graphene/bismuth titanate photocatalytic material, and it uses oxidation
Bismuth and titanium tetrachloride are raw material, and deionized water and BDO are reaction medium, the predecessor of bismuth titanates are obtained, afterwards with oxidation
Graphene aqueous solution is blended in heating response in autoclave and obtains graphene/bismuth titanate photocatalytic material.But this method
The catalyst prepared can only have preferable catalytic activity under visible light, it is impossible to suitable for full spectral conditions；And it is molten
Catalyst crystal formation is poor made from sol-gel, and avtive spot is few, has a strong impact on catalytic activity.
The A of CN 102941080 disclose a kind of Graphene/ bismuth oxide compound light catalyst and preparation method thereof, and its is main
It is characterized in bismuth oxide photocatalyst because its photo-generate electron-hole is easily in conjunction with making the reduction of its photocatalytic activity, pass through graphene
Modification on bismuth oxide photocatalyst surface, can significantly improve the separation of photo-generate electron-hole, so as to improve bismuth oxide light
The photocatalysis performance of catalyst.But catalyst made from this method can only still have preferable catalytic activity, nothing under visible light
Method is applied to full spectral conditions.
The content of the invention
Can not keep good catalytic activity under full spectral conditions for what existing photochemical catalyst was present, catalytic activity compared with
Low the problem of, the invention provides a kind of full spectral response type catalyst material and its production and use.The present invention passes through
Rationally design light urges the structure and composition of agent, has widened the application conditions of photochemical catalyst, make obtained photochemical catalyst it is ultraviolet,
It can be seen that and infrared band all have higher photocatalytic degradation efficiency.
Carried out by reach this purpose, the present invention uses following technical scheme：
In a first aspect, the invention provides a kind of preparation method of full spectral response type catalyst material, the catalyst
The preparation method of material comprises the following steps：
(1) bismuth salt is dissolved in reduction solvent, graphene oxide solution is added after being well mixed, stirring obtains mixed solution；
(2) the mixed solution heating obtained step (1) is reacted, and compound is obtained through post processing after reaction；
(3) compound for obtaining step (2) is made annealing treatment under protective atmosphere, obtains full spectral response type catalysis
Agent material.
Wherein, full spectral response type catalyst material of the present invention is graphene/bismuth composite photo-catalyst.
Below as currently preferred technical scheme, but the limitation of the technical scheme provided not as the present invention, pass through
Following technical scheme, can preferably reach and realize the technical purpose and beneficial effect of the present invention.
As currently preferred technical scheme, step (1) described bismuth salt is any in bismuth acetate, bismuth nitrate or Bismuth Octoate
It is a kind of or at least two combination, combination typical case but non-limiting examples have：The combination of bismuth acetate and bismuth nitrate, bismuth nitrate
With the combination of Bismuth Octoate, the combination of bismuth acetate, bismuth nitrate and Bismuth Octoate etc..
Preferably, step (1) the reduction solvent is dimethyl sulfoxide (DMSO) and/or DMF.
In the present invention, the reduction solvent has two effects：One is, as reaction dissolvent, to disperse bismuth salt, be conducive to solvent
The progress of thermal response；Two be, as reducing agent, in solvent thermal reaction, trivalent bismuth to be reduced to the bismuth nano particle for obtaining zeroth order.
In the present invention, if replaced using other kinds of solvent (in addition to dimethyl sulfoxide (DMSO) and DMF)
Reduce solvent, will not possess effective reducing power, it is impossible to obtain the bismuth nano particle of zeroth order, so can not be made to it is ultraviolet can
The catalyst of full spectral response type outside show.
Preferably, the addition of step (1) described bismuth salt is：Addition bismuth salt 5mg~30mg, example in every milliliter of reduction solvent
Such as 6mg, 8mg, 10mg, 12mg, 14mg, 16mg, 18mg, 20mg, 22mg, 24mg, 26mg or 28mg, it is not limited to institute
Other unrequited numerical value are equally applicable in the numerical value enumerated, the number range, and bismuth is added in preferably every milliliter reduction solvent
Salt 10mg~20mg.
As currently preferred technical scheme, step (1) is described well mixed to be carried out by the way of ultrasonic disperse.
Preferably, step (1) described graphene oxide solution is added under conditions of stirring and/or concussion.
Preferably, the concentration of step (1) described graphene oxide solution be 2mg/mL~10mg/mL, such as 3mg/mL,
4mg/mL, 5mg/mL, 6mg/mL, 7mg/mL, 8mg/mL or 9mg/mL etc., it is not limited to cited numerical value, the numerical value
In the range of other unrequited numerical value it is equally applicable.
Preferably, the addition of step (1) described graphene oxide solution is：Graphene oxide is set to account for catalyst material total
0.05wt%~10wt% of quality, such as 0.07wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%,
7wt%, 8wt% or 9wt% etc., it is not limited to other unrequited numerical value are same in cited numerical value, the number range
Sample is applicable.
Preferably, step (1) described mixing time be 20min~60min, such as 22min, 28min, 34min, 40min,
46min, 52min or 58min etc., it is not limited to other unrequited numerical value are same in cited numerical value, the number range
Sample is applicable, preferably 30min~35min.
As currently preferred technical scheme, step (2) described reaction temperature is 150 DEG C~200 DEG C, such as 155 DEG C,
160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C or 195 DEG C etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the number range.
Preferably, step (2) reaction time is 2h~24h, such as 3h, 5h, 7h, 10h, 13h, 15h, 17h, 20h
Or 22h etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
As currently preferred technical scheme, step (2) described last handling process successively include standing, separation of solid and liquid,
Wash and dry.
Preferably, the separation of solid and liquid is centrifugation.
Preferably, the drying is freeze-drying.Drying process of the present invention is carried out according to conventional mode, easily
Make material occur to reunite and caking phenomenon, and then influence subsequent anneal and catalytic performance.
As currently preferred technical scheme, step (3) described protective atmosphere is nitrogen atmosphere and/or argon gas atmosphere.
Preferably, the temperature of step (3) described annealing be 300 DEG C~800 DEG C, such as 305 DEG C, 350 DEG C, 400 DEG C,
450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C or 795 DEG C etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the number range, preferably 400 DEG C~600 DEG C.
Preferably, the time of step (3) described annealing be 0.5h~10h, such as 0.6h, 1h, 2h, 3h, 4h, 5h,
6h, 7h, 8h or 9h etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range,
Preferably 2h~6h.
Preferably, the pressure of step (3) described annealing be 0.001MPa~0.1MPa, such as 0.002MPa,
0.01MPa, 0.02MPa, 0.03MPa, 0.04MPa, 0.05MPa, 0.06MPa, 0.07MPa, 0.08MPa or 0.09MPa etc., but
It is not limited in other unrequited numerical value in cited numerical value, the number range equally applicable, preferably 0.005MPa~
0.05MPa。
In the present invention, the interaction between graphene and bismuth nano particle can be strengthened by carrying out annealing to compound
Power, at the same time, the oxy radical of graphene edge can chemically react with bismuth nano particle, be formed on nanometer level
Hetero-junctions, causes the change of structure, on the one hand, creates separation and transfer that suitable energy level is beneficial to electric charge, on the other hand utilizes
The great specific surface area of graphene, makes gained catalyst material have more avtive spots, and then improve its catalytic performance.
The temperature of the annealing should also be controlled within the specific limits, if annealing temperature is too high, catalyst is easily quenched
Activated centre, reduce catalytic performance；If annealing temperature is too low, it is unfavorable for the stroke of hetero-junctions, can also reduces catalytic performance.
As currently preferred technical scheme, step (3) is described made annealing treatment after, by grinding, obtain full light
Compose response type catalyst material.
As currently preferred technical scheme, the preparation method of the catalyst material comprises the following steps：
(1) bismuth salt is dissolved in reduction solvent dimethyl sulfoxide (DMSO) and/or DMF, wherein every milliliter of dimethyl
Bismuth salt 10mg~20mg is added in sulfoxide, added under agitation after ultrasonic disperse is well mixed concentration for 2mg/mL~
10mg/mL graphene oxide solution, makes graphene oxide account for 0.05wt%~10wt% of catalyst material gross mass, stirring
30min~35min obtains mixed solution；
(2) mixed solution for obtaining step (1) is heated to 150 DEG C~200 DEG C and reacted, and reacts 2h~24h, reaction
Compound is obtained after through standing, centrifugation, washing and freeze-drying successively；
(3) compound for obtaining step (2) is carried out under nitrogen atmosphere and/or argon gas atmosphere at 400 DEG C~600 DEG C
Make annealing treatment 2h~6h, the pressure of annealing is 0.005MPa~0.05MPa, then ground obtain full spectral response type catalysis
Agent material.
Second aspect is described complete the invention provides full spectral response type catalyst material made from above-mentioned preparation method
Spectral response type catalyst material has the catalytic activity of degradation of contaminant under ultraviolet light, visible ray and infrared light.
The third aspect, the invention provides the purposes of above-mentioned full spectral response type catalyst material, it is characterised in that described
Full spectral response type catalyst material is used for contaminant degradation field.Such as to pollutant Cr VI, methyl orange or Luo Danming
Degraded, it is not limited to listed field.
Compared with prior art, the invention has the advantages that：
The present invention reacts by using the reproducibility such as dimethyl sulfoxide (DMSO) solvent and bismuth salt, and annealed processing, can be made
Ultraviolet, visible and infrared band all have higher absorption photochemical catalyst, the catalyst under the full excitation of spectra to Cr VI,
Methyl orange or Luo Danming etc. pollutant have efficient photocatalytic degradation efficiency, in ultraviolet light, visible ray and Infrared irradiation
Its lower photocatalytic degradation efficiency is up to 100%.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of obtained full spectral response type catalyst material in the embodiment of the present invention 1；
Fig. 2 is the X-ray diffractogram of obtained full spectral response type catalyst material in the embodiment of the present invention 1；
Fig. 3 be in the embodiment of the present invention 1 obtained full spectral response type catalyst material ultraviolet, visible, infrared and
Catalytic performance figure (degraded methyl orange) under full spectrum；
Fig. 4 be in the embodiment of the present invention 1 obtained full spectral response type catalyst material ultraviolet, visible, infrared and
Catalytic performance figure (degraded Cr VI) under full spectrum；
Fig. 5 is obtained full catalytic performance of the spectral response type catalyst material under INFRARED SPECTRUM in the embodiment of the present invention 1
Figure (degraded Luo Danming)；
Fig. 6 (a) is that obtained full spectral response type catalyst material sacrifice agent under sunshine is deposited in the embodiment of the present invention 1
Photo is reacted during 0min in case；
Fig. 6 (b) is that obtained full spectral response type catalyst material sacrifice agent under sunshine is deposited in the embodiment of the present invention 1
Photo is reacted during 25min in case；
Fig. 7 is the scanning electron microscope (SEM) photograph of obtained full spectral response type catalyst material in the embodiment of the present invention 2；
Fig. 8 is the X-ray diffractogram of obtained full spectral response type catalyst material in the embodiment of the present invention 2；
Fig. 9 is the scanning electron microscope (SEM) photograph of obtained full spectral response type catalyst material in the embodiment of the present invention 4；
Figure 10 is the X-ray diffractogram of obtained full spectral response type catalyst material in the embodiment of the present invention 4.
Embodiment
For the present invention is better described, technical scheme is readily appreciated, below to the present invention further specifically
It is bright.But following embodiments is only the simple example of the present invention, the scope of the present invention is not represented or limits, this
Invention protection domain is defined by claims.
Specific embodiment of the invention part provides a kind of full spectral response type catalyst material and preparation method thereof, and it is made
Preparation Method comprises the following steps：
(1) bismuth salt is dissolved in reduction solvent, graphene oxide solution is added after being well mixed, stirring obtains mixed solution；
(2) the mixed solution heating obtained step (1) is reacted, and compound is obtained through post processing after reaction；
(3) compound for obtaining step (2) is made annealing treatment under protective atmosphere, obtains full spectral response type catalysis
Agent material.
It is below present invention typical case but non-limiting example：
Embodiment 1：
A kind of full spectral response type catalyst material and preparation method thereof is present embodiments provided, the preparation method is：
(1) 200mg bismuth acetates are weighed and are dissolved in 30mL dimethyl sulfoxide (DMSO)s, ultrasonic disperse is well mixed, the concentration for adding 2mL is
Mixed solution is obtained after 4mg/mL graphene oxide solution, stirring 30min；
(2) mixed solution for obtaining step (1) is transferred in ptfe autoclave, and 4h is reacted at 180 DEG C, quiet
Compound is obtained after putting, centrifuge, wash and being freeze-dried；
(3) compound for obtaining step (2) is in a nitrogen atmosphere in high annealing 2h at 500 DEG C, and reaction pressure is
0.05MPa, obtains full spectral response type catalyst material.
The scanning electron microscope (SEM) photograph of full spectral response type catalyst material is as shown in figure 1, its X-ray diffractogram obtained by the present embodiment
As shown in Fig. 2 it can be seen that graphene is wraps closely about bismuth Nanosurface, showing there is strong phase between the two
Interaction, while obtained catalyst material has good crystalline form.
Obtained full spectral response type catalyst material is used for methyl orange, Cr (VI) and sieve to concentration for 60mg/mL
Red name carries out catalytic degradation, as a result as shown in Fig. 3, Fig. 4 and Fig. 5, when the addition of catalyst material is 1g/L, can see
Go out, methyl orange and Cr (VI) are degradable after ultraviolet light 30min, methyl orange and Cr after radiation of visible light 40min
(VI) degradable, methyl orange and Cr (VI) are degradable after Infrared irradiation 50min, with higher application prospect.
Meanwhile, full spectral response type catalyst material is in the presence of sacrifice agent under sunshine made from the present embodiment
Catalytic performance such as Fig. 6 (a) and Fig. 6 (b) shown in, corresponding reaction photo when Fig. 6 (a) is 0min, Fig. 6 (b) is anti-after 25min
The photo answered, it can be seen that after sunshine irradiation 25min, methyl orange is degradable, and degradation rate reaches 100%.
Embodiment 2：
A kind of full spectral response type catalyst material and preparation method thereof is present embodiments provided, the preparation method is：
(1) 200mg bismuth nitrates are weighed and are dissolved in 30mL dimethyl sulfoxide (DMSO)s, ultrasonic disperse is well mixed, the concentration for adding 2mL is
Mixed solution is obtained after 2mg/mL graphene oxide solution, stirring 30min；
(2) mixed solution for obtaining step (1) is transferred in ptfe autoclave, and 12h is reacted at 160 DEG C,
Compound is obtained after standing, centrifuge, wash and being freeze-dried；
(3) compound for obtaining step (2) is under an argon atmosphere in high annealing 5h at 300 DEG C, and reaction pressure is
0.09MPa, obtains full spectral response type catalyst material.
The scanning electron microscope (SEM) photograph of full spectral response type catalyst material is as shown in fig. 7, its X-ray diffractogram obtained by the present embodiment
As shown in figure 8, as can be seen from the figure similar to Example 1, graphene is wraps closely about bismuth Nanosurface, show both it
Between there is strong interaction, while obtained catalyst material has good crystalline form.
Obtained full spectral response type catalyst material is used to carry out concentration for 60mg/mL methyl orange and Cr (VI)
Catalytic degradation, when the addition of catalyst material is 1g/L, it can be seen that methyl orange and Cr after ultraviolet light 35min
(VI) degradable, methyl orange and Cr (VI) are degradable after radiation of visible light 40min, the first after Infrared irradiation 55min
Base orange and Cr (VI) are degradable, with higher application prospect.
Embodiment 3：
A kind of full spectral response type catalyst material and preparation method thereof is present embodiments provided, the preparation method is：
(1) 300mg Bismuth Octoates are weighed and are dissolved in 20mL dimethyl sulfoxide (DMSO)s, ultrasonic disperse is well mixed, the concentration for adding 4mL is
Mixed solution is obtained after 4mg/mL graphene oxide solution, stirring 30min；
(2) mixed solution for obtaining step (1) is transferred in ptfe autoclave, and 24h is reacted at 200 DEG C,
Compound is obtained after standing, centrifuge, wash and being freeze-dried；
(3) compound for obtaining step (2) is under an argon atmosphere in high annealing 8h at 800 DEG C, and reaction pressure is
0.005MPa, obtains full spectral response type catalyst material.
Obtained full spectral response type catalyst material is used to carry out concentration for 60mg/mL methyl orange and Cr (VI)
Catalytic degradation, when catalyst material addition be 0.5g/L when, it can be seen that after ultraviolet light 40min methyl orange and
Cr (VI) is degradable, and methyl orange and Cr (VI) are degradable after radiation of visible light 45min, after Infrared irradiation 60min
Methyl orange and Cr (VI) are degradable, with higher application prospect.
Embodiment 4：
A kind of full spectral response type catalyst material and preparation method thereof is present embodiments provided, the preparation method is：
(1) 300mg bismuth acetates are weighed and are dissolved in 20mL dimethyl sulfoxide (DMSO)s, ultrasonic disperse is well mixed, the concentration for adding 4mL is
Mixed solution is obtained after 4mg/mL graphene oxide solution, stirring 30min；
(2) mixed solution for obtaining step (1) is transferred in ptfe autoclave, and 16h is reacted at 200 DEG C,
Compound is obtained after standing, centrifuge, wash and being freeze-dried；
(3) compound for obtaining step (2) is under an argon atmosphere in high annealing 5h at 600 DEG C, and reaction pressure is
0.005MPa, it is ground to obtain full spectral response type catalyst material.
The scanning electron microscope (SEM) photograph of full spectral response type catalyst material is as shown in figure 9, its X-ray diffractogram obtained by the present embodiment
As shown in Figure 10, it can be seen that similar to Example 1, graphene is wraps closely about bismuth Nanosurface, shows both
Between there is strong interaction, while obtained catalyst material has good crystalline form.
Obtained full spectral response type catalyst material is used to carry out concentration for 60mg/mL methyl orange and Cr (VI)
Catalytic degradation, when catalyst material addition be 1.5g/L when, it can be seen that after ultraviolet light 25min methyl orange and
Cr (VI) is degradable, and methyl orange and Cr (VI) are degradable after radiation of visible light 35min, after Infrared irradiation 45min
Methyl orange and Cr (VI) are degradable, with higher application prospect.
Embodiment 5：
A kind of full spectral response type catalyst material and preparation method thereof is present embodiments provided, the preparation method is：
(1) 200mg Bismuth Octoates are weighed and are dissolved in 30mL dimethyl sulfoxide (DMSO)s, ultrasonic disperse is well mixed, the concentration for adding 1mL is
Mixed solution is obtained after 4mg/mL graphene oxide solution, stirring 30min；
(2) mixed solution for obtaining step (1) is transferred in ptfe autoclave, and 12h is reacted at 160 DEG C,
Compound is obtained after standing, centrifuge, wash and being freeze-dried；
(3) compound for obtaining step (2) is under an argon atmosphere in high annealing 6h at 300 DEG C, and reaction pressure is
0.05MPa, it is ground to obtain full spectral response type catalyst material.
Obtained full spectral response type catalyst material is used to carry out concentration for 60mg/mL methyl orange and Cr (VI)
Catalytic degradation, when the addition of catalyst material is 1g/L, it can be seen that methyl orange and Cr after ultraviolet light 30min
(VI) degradable, methyl orange and Cr (VI) are degradable after radiation of visible light 40min, the first after Infrared irradiation 50min
Base orange and Cr (VI) are degradable, with higher application prospect.
Embodiment 6：
Present embodiments provide a kind of full spectral response type catalyst material and preparation method thereof, the preparation method except
100mg bismuth acetates are dissolved in 20mL dimethyl sulfoxide (DMSO)s in step (1), 35min is stirred；Reaction temperature is 150 DEG C in step (2),
Annealing temperature in step (3) is 400 DEG C, and annealing time is 9h, and annealing pressure is unclassified stores consumption and system outside 0.002MPa
Standby process is in the same manner as in Example 1.
Obtained full spectral response type catalyst material is used to carry out concentration for 60mg/mL methyl orange and Cr (VI)
Catalytic degradation, when the addition of catalyst material is 1g/L, it can be seen that methyl orange and Cr after ultraviolet light 40min
(VI) degradable, methyl orange and Cr (VI) are degradable after radiation of visible light 55min, the first after Infrared irradiation 65min
Base orange and Cr (VI) are degradable, with higher application prospect.
Embodiment 7：
Present embodiments provide a kind of full spectral response type catalyst material and preparation method thereof, the preparation method except
600mg bismuth acetates are dissolved in outside 20mL dimethyl sulfoxide (DMSO)s, stirring 40min in step (1), unclassified stores consumption and preparation process are equal
It is in the same manner as in Example 1.
Obtained full spectral response type catalyst material is used to carry out concentration for 60mg/mL methyl orange and Cr (VI)
Catalytic degradation, when the addition of catalyst material is 1g/L, it can be seen that methyl orange and Cr after ultraviolet light 25min
(VI) degradable, methyl orange and Cr (VI) are degradable after radiation of visible light 35min, the first after Infrared irradiation 45min
Base orange and Cr (VI) are degradable, with higher application prospect.
Comparative example 1：
This comparative example provides a kind of photocatalyst material and preparation method thereof, and the preparation method is except in step (1)
Solvent for use is that unclassified stores consumption is same as Example 1 with preparation method outside ethylene glycol.
Photocatalyst material made from this comparative example, obtained composite catalyst is poor in the catalytic performance of visible region,
Infrared light district does not have catalytic performance, without full spectral response performance, therefore can not make full use of sunshine, reaches pollution degradation
The purpose of thing.
Comparative example 2：
This comparative example provides a kind of photocatalyst material and preparation method thereof, and the preparation method is except without step
(3) outside the annealing in, unclassified stores consumption is same as Example 1 with preparation method.
Photocatalyst material made from this comparative example, obtained complex catalyst is urged visible region and infrared light district
Change performance extreme difference, without full spectral response performance, therefore sunshine can not be made full use of, reach the purpose of degradation of contaminant.
Comparative example 3：
This comparative example provides a kind of photocatalyst material and preparation method thereof, and the preparation method is except without step
(3) temperature of the annealing in is too low, is 200 DEG C outer, unclassified stores consumption is same as Example 1 with preparation method.
Photocatalyst material made from this comparative example, obtained complex catalyst visible region catalytic performance compared with
Difference, does not have catalytic performance in infrared light district, thus does not possess full spectral response performance, therefore can not make full use of sunshine, reaches
To the purpose of degradation of contaminant.
Comparative example 4：
This comparative example provides a kind of photocatalyst material and preparation method thereof, and the preparation method is except without step
(3) temperature of the annealing in is too high, is 1000 DEG C outer, unclassified stores consumption is same as Example 1 with preparation method.
Photocatalyst material made from this comparative example, obtained complex catalyst is urged visible region and infrared light district
Change performance poor, thus do not possess full spectral response performance, therefore sunshine can not be made full use of, reach degradation of contaminant
Purpose.
The result of summary embodiment and comparative example can be seen that the present invention by using reproducibility solvent (dimethyl
Sulfoxide and DMF) reacted with bismuth salt, and annealed processing, it can be made in ultraviolet, visible and infrared band all
Photochemical catalyst with higher absorption, the catalyst has height under the full excitation of spectra to the pollutant such as methyl orange and Cr (VI)
The photocatalytic degradation efficiency of effect, its photocatalytic degradation efficiency is up to 100% under ultraviolet light, visible ray and Infrared irradiation.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. a kind of preparation method of full spectral response type catalyst material, it is characterised in that the preparation side of the catalyst material
Method comprises the following steps：
(1) bismuth salt is dissolved in reduction solvent, graphene oxide solution is added after being well mixed, stirring obtains mixed solution；
(2) the mixed solution heating obtained step (1) is reacted, and compound is obtained through post processing after reaction；
(3) compound for obtaining step (2) is made annealing treatment under protective atmosphere, obtains full spectral response type catalyst material
Material.
2. preparation method according to claim 1, it is characterised in that step (1) described bismuth salt be bismuth acetate, bismuth nitrate or
Any one in Bismuth Octoate or at least two combination；
Preferably, step (1) the reduction solvent is dimethyl sulfoxide (DMSO) and/or DMF；
Preferably, the addition of step (1) described bismuth salt is：Addition bismuth salt 5mg~30mg in every milliliter of reduction solvent, be preferably
Addition bismuth salt 10mg~20mg in every milliliter of reduction solvent.
3. preparation method according to claim 1 or 2, it is characterised in that step (1) is described well mixed using ultrasound point
Scattered mode is carried out；
Preferably, step (1) described graphene oxide solution is added under conditions of stirring and/or concussion；
Preferably, the concentration of step (1) described graphene oxide solution is 2mg/mL~10mg/mL；
Preferably, the addition of step (1) described graphene oxide solution is：Graphene oxide is set to account for catalyst material gross mass
0.05wt%~10wt%；
Preferably, step (1) described mixing time is 20min~60min, preferably 30min~35min.
4. the preparation method according to claim any one of 1-3, it is characterised in that step (2) described reaction temperature is 150
DEG C~200 DEG C；
Preferably, step (2) reaction time is 2h~24h.
5. the preparation method according to claim any one of 1-4, it is characterised in that step (2) last handling process according to
It is secondary including standing, separation of solid and liquid, washing and dry；
Preferably, the separation of solid and liquid is centrifugation；
Preferably, the drying is freeze-drying.
6. the preparation method according to claim any one of 1-5, it is characterised in that step (3) described protective atmosphere is nitrogen
Gas atmosphere and/or argon gas atmosphere；
Preferably, the temperature of step (3) described annealing is 300 DEG C~800 DEG C, preferably 400 DEG C~600 DEG C；
Preferably, the time of step (3) described annealing is 0.5h~10h, preferably 2h~6h；
Preferably, the pressure of step (3) described annealing be 0.001MPa~0.1MPa, preferably 0.005MPa~
0.05MPa。
7. the preparation method according to claim any one of 1-6, it is characterised in that step (3) is described to be made annealing treatment
Afterwards, by grinding, full spectral response type catalyst material is obtained.
8. the preparation method according to claim any one of 1-7, it is characterised in that the preparation method of the catalyst material
Comprise the following steps：
(1) bismuth salt is dissolved in reduction solvent dimethyl sulfoxide (DMSO) and/or DMF, wherein every milliliter of dimethyl sulfoxide (DMSO)
Middle addition bismuth salt 10mg~20mg, adds concentration for 2mg/mL~10mg/mL under agitation after ultrasonic disperse is well mixed
Graphene oxide solution, graphene oxide is accounted for 0.05wt%~10wt% of catalyst material gross mass, stirring 30min~
35min obtains mixed solution；
(2) mixed solution for obtaining step (1) is heated to 150 DEG C~200 DEG C and reacted, and reacts 2h~24h, is passed through after reaction
Obtain compound through standing, centrifugation, washing and freeze-drying successively afterwards；
(3) compound for obtaining step (2) is annealed under nitrogen atmosphere and/or argon gas atmosphere at 400 DEG C~600 DEG C
Handle 2h~6h, the pressure of annealing is 0.005MPa~0.05MPa, then ground obtain full spectral response type catalyst material
Material.
9. full spectral response type catalyst material, its feature made from the preparation method according to claim any one of 1-8
It is, the full spectral response type catalyst material has the catalysis of degradation of contaminant under ultraviolet light, visible ray and infrared light
Activity.
10. the purposes of full spectral response type catalyst material according to claim 9, it is characterised in that the full spectrum
Response type catalyst material is used for contaminant degradation field.
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