CN108479777A - A kind of preparation method and applications of attapulgite composite photo-catalyst - Google Patents
A kind of preparation method and applications of attapulgite composite photo-catalyst Download PDFInfo
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- CN108479777A CN108479777A CN201810262800.9A CN201810262800A CN108479777A CN 108479777 A CN108479777 A CN 108479777A CN 201810262800 A CN201810262800 A CN 201810262800A CN 108479777 A CN108479777 A CN 108479777A
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- attapulgite
- catalyst
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- composite photo
- transition metal
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 60
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims description 31
- 239000011941 photocatalyst Substances 0.000 title claims description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- 238000004176 ammonification Methods 0.000 claims abstract description 11
- 239000004927 clay Substances 0.000 claims abstract description 9
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- -1 Transition metal salt Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 26
- 229910021529 ammonia Inorganic materials 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 7
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract 2
- 230000020477 pH reduction Effects 0.000 abstract 2
- 239000011229 interlayer Substances 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 26
- 239000004575 stone Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 239000012065 filter cake Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 238000009413 insulation Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 231100000749 chronicity Toxicity 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention belongs to photocatalytic synthesis ammonification technical field, more particularly to the preparation method and applications of a kind of modified attapulgite/transition metal oxide nano composite material.Preparation method includes：(1) it takes the Concave-convex clay rod purified to carry out acidification, makes H+Displace the partial cation and interlayer portion cation in attapulgite octahedral structure；(2) Concave-convex clay rod after acidification is put into transition metal salt solution, is fully reacted in 60~100 DEG C of water-bath；(3) above-mentioned reaction solution is placed in microwave hydrothermal chemical reaction instrument and is reacted, be then centrifuged for, wash, finished product is obtained after dry.The present invention can apply in photocatalytic synthesis ammonification field, compared with traditional industry synthetic ammonia, preparation method is simple, and energy consumption is greatly lowered using modified attapulgite/transition metal oxide as catalyst.
Description
Technical field
The invention belongs to photocatalytic synthesis ammonification technical fields, and in particular to a kind of visible light-responded attapulgite and transition gold
Belong to oxide and builds hetero-junctions as the nano material of active component, preparation method and its application in photocatalytic synthesis ammonification.
Background technology
Ammonia occupies very important status as a kind of important inorganic chemical product in national economy production, however,
In the industrial production, ammonia is synthesized by Haber-Bosh techniques under extreme condition (673-873K, 20-40MPa).Industry
Synthetic ammonia process is very big to the consumption of fossil fuel, inevitably causes a large amount of CO2Discharge.Therefore, in temperate condition
It is lower that nitrogen is reduced to ammonia (NH3) it is urgent problem.
The exploitation of low temperature, low pressure, effective catalyst is the key that reduce synthesis ammonia energy consumption, the sustainable fixed nitrogen of exploitation green
Process is challenging and chronicity a target.In recent years, it is converted solar energy into using solar energy photocatalytic technology
Chemical energy is realized light fixed nitrogen synthesis ammonia and is concerned.As photochemical catalyst, it is necessary to which it is a large amount of to generate to effectively absorb solar energy
Electric charge carrier (electron hole pair), these electric charge carriers of quick separating are compound to reduce, strong adsorption reactant so that
It is reacted with migration carrier, and with the valence band and conduction band for being suitble to oxidation and reduction reaction.The ammonia of light fixed nitrogen synthesis at present is urged
Agent mostly only has absorption to ultraviolet portion, develops the catalyst for having catalytic activity to the visible above light of 500nm or one
Challenge.
Concave-convex clay rod (abbreviation ATP) is a kind of natural clay mineral of zeopan containing Shuifu County, and it is special to have
Fibrous crystalline structure, unique structure impart the physicochemical properties such as its large specific surface area, adsorption capacity are strong and Saline alkali tolerance is good.
In natural forming process, crystal magnesium, aluminium ion can be substituted by transition metal ions such as iron for it, be formed containing a small amount of ferro element etc.
The attapulgite naturally adulterated, to make a large amount of visible light in its absorbable sunlight.But natural attapulgite clay visible light
Responding ability is poor, and photocatalysis efficiency is relatively low, visible light-responded in order to achieve, and improves catalytic efficiency, needs artificially to change it
The modifications such as property, doping, load, can preferably apply in photocatalytic synthesis ammonification technical field.
Invention content
In order to solve synthesis ammonia exacting terms, light fixed nitrogen synthetic ammonia catalyst mostly only has absorption to ultraviolet portion
Technical problem, it is multiple with microwave-hydrothermal method synthesis transition metal oxide/modified attapulgite nanometer that the present invention provides a kind of
Condensation material, that is, attapulgite composite photo-catalyst, catalyst obtained can be under the irradiations of visible light N2Turn to the greatest extent
It is melted into NH3.Photocatalytic synthesis ammonification yield is made it through by technological parameters such as optimizing raw material proportioning, hydrothermal temperature and hydro-thermal times
It is maximum.
The present invention solves technical problem and adopts the following technical scheme that：
A kind of preparation method of attapulgite composite photo-catalyst provided by the invention, includes the following steps：
(1) Concave-convex clay rod purified is taken to be added in 3mol/L hydrochloric acid solutions, ultrasonic dissolution is placed on 70 DEG C
It in water-bath, after carrying out 10h heat treatments, filters, washing is dried to obtain attapulgite pretreatment product；
Wherein, the volume of hydrochloric acid solution and the mass ratio of attapulgite are：100mL：2g；Wherein, hydrochloric acid solution is to adopt
With 35% analytically pure hydrochloric acid at 3mol/L.
(2) step (1) pretreated attapulgite is put into transition metal salt solution, in 60~100 DEG C of water-bath
It is fully reacted in pot；Wherein, optimization temperature is 70 DEG C.
Wherein, transition metal salt can be any one in Zn, Fe, Mn, Cu salt；The salting liquid of transition metal can be
The nitrate of transition metal, sulfate, the aqueous solution of any one in chloride；As an example, the transition metal salt can
Think FeCl3。
And the amount of the substance of transition metal salt and the mass ratio of modified attapulgite can be 0.0015~0.003mol:
1g。
(3) reaction solution in step (2) is transferred in 100mL reaction kettles, is placed in microwave hydrothermal chemical reaction instrument,
1~3h is reacted at 160~200 DEG C, is then filtered, and washs, transition metal oxide/modified attapulgite nanometer is obtained after drying
Composite finished product, i.e. attapulgite composite photo-catalyst.
Wherein, product after microwave hydrothermal is by repeatedly washing, to eliminate impurity, and at 60~100 DEG C drying 12~
24h。
The present invention also provides a kind of application of attapulgite composite photo-catalyst, the composite photo-catalyst is urged for light
Chemical combination ammonification.
The application process is：The attapulgite composite photo-catalyst for weighing preparation is dissolved in 100mL and (wherein contains 20%
Methanol is as hole trapping agents) in deionized water, then it is then added in photocatalytic reaction device, N2With the flow velocity of 60mL/min
It is passed through reaction unit, leads to N2Xenon lamp after 30min using 300W is irradiated as analog light source, and it is below ultraviolet to filter off 420nm
Light, it is ensured that only visible light exists, and 5mL samples are collected every 20min, and Nessler's reagent is added, fully extracts upper layer after reaction
Clear liquid tests its absorbance with ultraviolet spectrometer under 420nm wavelength.
Compared with the prior art, the present invention has the beneficial effect that：
1, transition metal oxide/modified attapulgite is prepared using the method that water-bath is combined with microwave hydrothermal in the present invention
Stone nanocomposite, synthetic method is simple, convenient, while being modified to attapulgite, not only makes attapulgite realization can
Light-exposed response also makes excessive transition metal salt under conditions of microwave hydrothermal, and oxo transition metal is formed on attapulgite surface
Compound constructs hetero-junctions with it；
2, modified attapulgite and transition metal oxide all have good absorption to light in the present invention, can both be used as electricity
Sub- donor also can be used as electron acceptor, light induced electron can be made to be conducted faster, and the two is configured to hetero-junctions, be conducive to urge
Change active raising；
3, present invention employs natural clay mineral material attapulgites as photocatalysis synthetic ammonia catalyst, surface class
The microcellular structure of molecular sieve promotes to N2Absorption, while reducing cost, while saving energy consumption, and realize mild
Under the conditions of nitrogen is reduced to ammonia.
Present invention will be further explained below with reference to the attached drawings and examples.
Description of the drawings
Fig. 1 is Fe2O3, the 40%Fe for preparing of modified ATP and embodiment 12O3The XRD spectra of/ATP samples；
Fig. 2 is 40%Fe prepared by embodiment 12O3The TEM photos of/ATP sample 100nm scale ranges；
Fig. 3 is 40%Fe prepared by embodiment 12O3The TEM photos of/ATP sample 10nm scale ranges；
Fig. 4 is modification ATP, Fe prepared by embodiment 12O3, 40%Fe2O350%Fe prepared by/ATP and example 42O3/
60%Fe prepared by ATP, example 52O3/ ATP samples are to nitrogen also virgin curve.
Specific implementation mode
For the preferred optimum formula of embodiment and technical process, invention content is further elaborated on.
Embodiment 1
The attapulgite for weighing 2g first is dissolved in the hydrochloric acid solution of 100ml 3mol/L, and ultrasonic dissolution is placed on water-bath
In, it after handling 10h at 70 DEG C, is filtered with circulation vacuum pump, filter cake through fully washing, dry at 60 DEG C, obtains bumps by 16h
Stick stone pretreatment product；Then 0.0015mol iron chloride is taken to be placed in the 100mL beakers containing 50mL deionized waters, stirring is molten
Above-mentioned pretreated attapulgite 1g is added after solution, is again stirring for dissolving, is put in 70 DEG C of water-bath and is stirred to react 8h；Most
The reaction solution in beaker is transferred to 160 DEG C of insulation reaction 2h in 100mL microwave hydrothermal reaction kettles afterwards, with circulating vacuum pumping
Filter, filter cake through fully washing, dry at 60 DEG C, obtains iron oxide/modified attapulgite stone composite material, i.e. 40%Fe by 16h2O3/
ATP samples.
X-ray powder diffraction experiment is carried out to the iron oxide prepared by the present embodiment/modified attapulgite stone composite material, and
Its pattern and structure are observed under transmission electron microscope, it is as shown in Figure 1 with the XRD spectrum of modified attapulgite, iron oxide:Modification is recessed
The characteristic diffraction peak of convex stick stone and iron oxide occurs in iron oxide/modified attapulgite stone composite material, illustrates the composite material
It is successfully prepared out.40%Fe2O3The TEM photos of/ATP samples are as shown in Figure 2 and Figure 3.It can be seen from the figure that iron oxide
It is more uniformly combined with each other with modified attapulgite, it is consistent with the result of XRD.Modified attapulgite can be clearly seen in Fig. 2
Stone shows that the part of the metal oxide being precipitated, Fig. 3 HRTEM can be seen that the iron oxide that highly crystalline is precipitated and attapulgite are close
It is combined together, is configured to hetero-junctions.
The present invention also provides the methods that above-mentioned composite material is used for photocatalytic synthesis ammonification：Weigh the iron oxide of preparation/change
Property attapulgite 0.05g be dissolved in 100mL (wherein containing 20% methanol as hole trapping agents) deionized water, then again plus
Enter into photocatalytic reaction device, N2It is passed through reaction unit with the flow velocity of 60mL/min, leads to N2Made with the xenon lamp of 300W after 30min
It is irradiated for analog light source, filters off 420nm ultraviolet lights below, it is ensured that only visible light exists, and 5mL is collected every 20min
Sample is added Nessler's reagent, fully extracts supernatant liquor after reaction, its suction is tested under 420nm wavelength with ultraviolet spectrometer
Luminosity measures modified ATP, Fe2O3, 40%Fe2O3The NH of/ATP, sample3Formation curve as shown in figure 4, it can be seen from the figure that
In 1h, modified ATP generates NH3About 70 μm of ol/L, Fe2O3Generate NH3About 100 μm of ol/L, and 40%Fe2O3/ ATP samples
Generate NH3Up to 150 μm of ol/L or more, and 50%Fe2O3/ ATP samples generate NH3Up to 180 μm of ol/L.
Embodiment 2
The attapulgite for weighing 2g first is dissolved in the hydrochloric acid solution of 100ml 3mol/L, and ultrasonic dissolution is placed on water-bath
In, it after handling 10h at 70 DEG C, is filtered with circulation vacuum pump, filter cake through fully washing, dry at 80 DEG C, obtains bumps by 15h
Stick stone pretreatment product；Then 0.002mol iron chloride is taken to be placed in the 100mL beakers containing 50mL deionized waters, stirring and dissolving
After above-mentioned pretreated attapulgite 1g is added, be again stirring for dissolving, be put in 70 DEG C of water-bath and be stirred to react 8h；Finally
Reaction solution in beaker is transferred to 160 DEG C of insulation reaction 3h in 100mL microwave hydrothermal reaction kettles, is filtered with circulation vacuum pump,
Filter cake is through fully washing, and 18h is dried at 80 DEG C, obtains iron oxide/modified attapulgite stone composite material, subsequent detection is as implemented
Example 1.
Embodiment 3
The Concave-convex clay rod for weighing 2g first is dissolved in the hydrochloric acid solution of 100mL 3mol/L, and ultrasonic dissolution is placed on water
It in bath, after handling 10h at 70 DEG C, is filtered with circulation vacuum pump, filter cake through fully washing, dry at 70 DEG C, obtains by 16h
Concave-convex clay rod pretreatment product；Then 0.003mol iron chloride is taken to be placed in the 100mL beakers containing 50mL deionized waters,
Above-mentioned pretreated Concave-convex clay rod 1g is added after stirring and dissolving, is again stirring for dissolving, is put in 70 DEG C of water-bath and stirs
Mix reaction 10h；The reaction solution in beaker is finally transferred to 170 DEG C of insulation reaction 3h in 100mL microwave hydrothermal reaction kettles, with following
Ring vacuum pump filters, and filter cake through fully washing, dry at 70 DEG C, obtains iron oxide/modified attapulgite stone composite material by 16h,
Subsequent detection such as embodiment 1.
Embodiment 4
The attapulgite for weighing 2g first is dissolved in the hydrochloric acid solution of 100mL 3mol/L, and ultrasonic dissolution is placed on water-bath
In, it after handling 10h at 70 DEG C, is filtered with circulation vacuum pump, filter cake through fully washing, dry at 60 DEG C, obtains bumps by 15h
Stick stone pretreatment product；Then 0.0018mol iron chloride is taken to be placed in the 100mL beakers containing 50mL deionized waters, stirring is molten
Above-mentioned pretreated attapulgite 1g is added after solution, is again stirring for dissolving, is put in 70 DEG C of water-bath and is stirred to react 10h；
The reaction solution in beaker is finally transferred to 180 DEG C of insulation reaction 2h in 100mL microwave hydrothermal reaction kettles, with circulating vacuum pumping
Filter, filter cake dry at 60 DEG C through fully washing, obtain iron oxide/modified attapulgite stone composite material, subsequent detection is such as 24 hours
Embodiment 1.
Embodiment 5
The attapulgite for weighing 2g first is dissolved in the hydrochloric acid solution of 100mL 3mol/L, and ultrasonic dissolution is placed on water-bath
In, it after handling 10h at 70 DEG C, is filtered with circulation vacuum pump, filter cake through fully washing, dry at 70 DEG C, obtains bumps by 16h
Stick stone pretreatment product；Then 0.0022mol iron chloride is taken to be placed in the 100mL beakers containing 50mL deionized waters, stirring is molten
Above-mentioned pretreated attapulgite 1g is added after solution, is again stirring for dissolving, is put in 70 DEG C of water-bath and is stirred to react 8h；Most
The reaction solution in beaker is transferred to 200 DEG C of insulation reaction 1h in 100mL microwave hydrothermal reaction kettles afterwards, with circulating vacuum pumping
Filter, filter cake through fully washing, dry at 100 DEG C, obtains iron oxide/modified attapulgite stone composite material, subsequent detection is such as by 12h
Embodiment 1.
Comparative example 1
The attapulgite for weighing 2g first is dissolved in the hydrochloric acid solution of 100ml 3mol/L, and ultrasonic dissolution is placed on water-bath
In, it after handling 10h at 70 DEG C, is filtered with circulation vacuum pump, filter cake through fully washing, dry at 60 DEG C, obtains bumps by 16h
Stick stone pretreatment product；Then 0.0015mol iron chloride is taken to be placed in the 100mL beakers containing 50mL deionized waters, stirring is molten
Above-mentioned pretreated attapulgite 1g is added after solution, is again stirring for dissolving, is put in 70 DEG C of water-bath and is stirred to react 8h；So
It is filtered afterwards with circulation vacuum pump, filter cake is through fully washing, and 16h is dried at 60 DEG C, and it is concave-convex to obtain common water-bath iron oxide/modification
Stick stone composite material.It weighs above-mentioned composite material 0.05g and measures generation NH in 1h for photocatalytic synthesis ammonification3About 120 μm of ol/
L.
Since water-bath may only have least a portion of metal ion and the H in the attapulgite of acid processing+There are displacements
Reaction, and further microwave hydrothermal reaction makes more H+Displacement occurs with metal ion to react, and then makes the Al being displaced3 +, Mg2+Octahedral site, by Fe3+Filling makes its lattice rebuild while under the conditions of microwave hydrothermal, basic to restore, thus through into
The microwave hydrothermal composite material obtained by the reaction of one step generates NH for photocatalytic synthesis ammonification3Up to 150 μm of ol/L or more.
Claims (8)
1. a kind of preparation method of attapulgite composite photo-catalyst, it is characterised in that：The preparation method includes the following steps：
(1) Concave-convex clay rod purified is taken to be added in 3mol/L hydrochloric acid solutions, ultrasonic dissolution is placed on 70 DEG C of water-baths
Middle progress 10h processing, is then filtered, and washing is dried to obtain attapulgite pretreatment product；
(2) step (1) pretreated attapulgite is put into transition metal salt solution, is placed in water-bath and fully reacts；
(3) reaction solution in step (2) is transferred in 100mL reaction kettles, is placed in microwave hydrothermal chemical reaction instrument and reacts, so
After filter, wash, attapulgite composite photo-catalyst is obtained after drying.
2. the preparation method of attapulgite composite photo-catalyst as described in claim 1, it is characterised in that：Step (1) is described
The volume of hydrochloric acid solution and the mass ratio of attapulgite are：100mL：2g.
3. the preparation method of attapulgite composite photo-catalyst as described in claim 1, it is characterised in that：Step (2) is described
Transition metal salt is any one in Zn, Fe, Mn, Cu salt；The salting liquid of transition metal is the nitrate of transition metal, sulfuric acid
Salt, the aqueous solution of any one in chloride.
4. the preparation method of attapulgite composite photo-catalyst as described in claim 1, it is characterised in that：Step (2) is described
The amount of the substance of transition metal salt and the mass ratio of modified attapulgite are 0.0015~0.003mol:1g.
5. the preparation method of attapulgite composite photo-catalyst as described in claim 1, it is characterised in that：Step (2) is described
Water-bath temperature is：60~100 DEG C.
6. the preparation method of attapulgite composite photo-catalyst as described in claim 1, it is characterised in that：Step (3) is described
Microwave hydrothermal reaction temperature is：160~200 DEG C；Reaction time is：1~3h.
7. the preparation method of attapulgite composite photo-catalyst as described in claim 1, it is characterised in that：Step (3) is described
Product after microwave hydrothermal dries 12 at 60~100 DEG C~for 24 hours.
8. a kind of application of attapulgite composite photo-catalyst prepared by method as described in claim 1, it is characterised in that：It is described
Composite photo-catalyst is used for photocatalytic synthesis ammonification.
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