CN110252375A - A kind of iron, nitrogen, the Titanium dioxide/active carbon compound of cobalt codope, preparation method and as photocatalyst applications - Google Patents
A kind of iron, nitrogen, the Titanium dioxide/active carbon compound of cobalt codope, preparation method and as photocatalyst applications Download PDFInfo
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- CN110252375A CN110252375A CN201910557377.XA CN201910557377A CN110252375A CN 110252375 A CN110252375 A CN 110252375A CN 201910557377 A CN201910557377 A CN 201910557377A CN 110252375 A CN110252375 A CN 110252375A
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- titanium dioxide
- nitrogen
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- iron
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 132
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 94
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 65
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 47
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 46
- 239000010941 cobalt Substances 0.000 title claims abstract description 46
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 150000001722 carbon compounds Chemical class 0.000 title claims abstract description 21
- 239000011941 photocatalyst Substances 0.000 title abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 38
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 28
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 230000007062 hydrolysis Effects 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 18
- 239000003610 charcoal Substances 0.000 claims description 17
- 238000006731 degradation reaction Methods 0.000 claims description 17
- 230000015556 catabolic process Effects 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 8
- 244000060011 Cocos nucifera Species 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 23
- 150000001721 carbon Chemical class 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000012153 distilled water Substances 0.000 description 13
- 238000001354 calcination Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000002019 doping agent Substances 0.000 description 7
- 239000002250 absorbent Substances 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/40—
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of iron, nitrogen, the Titanium dioxide/active carbon compound of cobalt codope, preparation methods and its as photocatalyst applications, belong to titanium dioxide field of compounding.A kind of iron, nitrogen, cobalt codope Titanium dioxide/active carbon compound preparation method, comprising the following steps: 1) butyl titanate is dissolved in dehydrated alcohol, obtains mixed liquor A；2) ferric nitrate, urea and cobalt nitrate are dissolved in mixed liquor A, obtain mixed liquid B；3) it disperses mixed liquid B in active carbon, obtains loaded article A；4) loaded article A is placed in the atmosphere of water vapour and dehydrated alcohol steam, obtains loaded article B；5) loaded article B is calcined, obtains the Titanium dioxide/active carbon compound of iron, nitrogen, cobalt codope.The preparation method controls the molding and granular size of titanium dioxide on the activated carbon by controlling the hydrolysis rate of titanate esters, obtains ideal photochemical catalyst.
Description
Technical field
The invention belongs to titanium dioxide field of compounding, the Titanium dioxide/active carbon of especially a kind of iron, nitrogen, cobalt codope
Compound, preparation method and its as photocatalyst applications.
Background technique
With being continuously increased for car ownership, tail gas pollution problems demand is solved.For this purpose, photochemical catalyst titanium dioxide by
In its high catalytic activity, chemical stability and nontoxic characteristic, make it in field of exhaust gas purification by favor.For this purpose, people
Have developed photocatalytic degradation tail gas material, wherein the light catalyzed coating of load nano-titanium dioxide just belongs to one of which,
Nano-titanium dioxide is used as photochemical catalyst, can most pollutants in catalysis oxidation air, catabolite is nothing
The harmless small-molecule substance of poison.
Currently, existing photocatalysis tail gas clean-up processing means use, but higher to light source requirements, and degradation efficiency and catalysis
Agent utilization rate is lower.Photochemical catalyst is when degrading air pollutants, it is necessary first to which active catalyst sites are had with pollutant
Effect contact, and nano-titanium dioxide surface higher can easily reunite, and reduce the area that active site is contacted with pollutant, greatly
Affect degradation efficiency.Use porous material-active carbon to load as carrier to catalyst, can not only prevent nanometer two
The reunion of titanium oxide, and absorption-degradation synergistic effect can be formed, further increase removal efficiency.Preparation modification at present is mixed
Miscellaneous titanium dioxide-active carbon composite photo-catalyst method is broadly divided into ball-milling method, sol-gal process and hydro-thermal method.Wherein it is modified
Hydrolysis rate in the load capacity of titanium dioxide, preparation process is all not easy to control, and the composite photo-catalyst being prepared is difficult to send out
Wave absorption-degradation synergistic effect.Such as patent CN108786732 is prepared for a kind of titanium dioxide/biology using sol-gal process
Activated carbon composite photo-catalyst, such photochemical catalyst are not modified processing to titanium dioxide, when just for ultraviolet light
Degradation efficiency is higher, but degradation efficiency is lower under visible light, lower to light source utilization rate, and limits its scope of application.Specially
Iron, the nitrogen of sharp CN103240110 preparation are co-doped with Titanium dioxide/active carbon photocatalyst, use the preparation method of sol impregnation,
The hydrolysis rate of the titanium dioxide of preparation process is difficult to control, and sol impregnation is easy to cause superfluous colloidal sol spontaneous hydrolysis to form trip
Make from titanium dioxide granule activated carbon supported incomplete.
Summary of the invention
It is an object of the invention to overcome the above-mentioned prior art, the titanium dioxide of a kind of iron, nitrogen, cobalt codope is provided
Titanium/activity Carbon composites, preparation method and its as photocatalyst applications.
In order to achieve the above objectives, the present invention is achieved by the following scheme:
A kind of iron, nitrogen, cobalt codope Titanium dioxide/active carbon compound preparation method, comprising the following steps:
1) butyl titanate is dissolved in dehydrated alcohol, adjusting pH is 1-2, obtains mixed liquor A；Wherein, butyl titanate and nothing
The volume ratio of water-ethanol is 1:(4-5)；
2) ferric nitrate, urea and cobalt nitrate are dissolved in mixed liquor A, obtain mixed liquid B；Wherein, ferric nitrate, urea, nitre
The mass ratio of sour cobalt and butyl titanate is (0.04-0.06): (0.06-0.10): (0.05-0.09): 1；
3) it disperses mixed liquid B in active carbon, obtains loaded article A；
4) loaded article A is placed in the atmosphere of water vapour and dehydrated alcohol steam, butyl titanate hydrolyzes, and is loaded
Object B；Wherein, the atmosphere of the water vapour and dehydrated alcohol steam is provided by the water and dehydrated alcohol being placed in confined space, nothing
The volume ratio of water-ethanol and water is 1:(1-3)；
5) it by after loaded article B washing, drying, grinding, is placed at 250-350 DEG C and calcines 1-2h, obtain iron, nitrogen, cobalt and be co-doped with
Miscellaneous Titanium dioxide/active carbon compound.
Further, the active carbon in step 3) is the cocoanut active charcoal by base extraction.
Further, the mass ratio that the mixed liquid B and active carbon in active carbon are dispersed in step 3) is 3:1.
Further, it disperses mixed liquid B in active carbon in step 3), 10-60min is placed in subnormal ambient, obtain
To loaded article A.
Further, the temperature that butyl titanate hydrolyzes is 30 DEG C, hydrolysis time 8-12h.
Further, the ratio between volume of total volume and confined space of dehydrated alcohol and water is 1:10 in step 4).
A kind of iron, nitrogen, cobalt codope Titanium dioxide/active carbon compound the preparation method iron, nitrogen, the cobalt that are prepared
The Titanium dioxide/active carbon compound of codope.
Further, the application as photochemical catalyst catalytic degradation nitrogen oxides.
Compared with prior art, the invention has the following advantages:
Iron of the invention, nitrogen, cobalt codope Titanium dioxide/active carbon compound preparation method, to preparation titanium dioxide
The conventional sol-gel processes of titanium are improved, and the titanium dioxide granule of conventional sol gel method preparation is coarse, and crystal form is only logical
Calcination temperature is crossed to control, since calcination temperature cannot be too high when active carbon is as carrier, otherwise will affect the absorption of active carbon
Intensity；The crystal form of titanium dioxide is not perfect when calcination temperature is lower, influences its catalytic effect.This method passes through control titanate esters
Hydrolysis rate controls the molding and granular size of titanium dioxide on the activated carbon, avoids crystal form by calcination temperature single factor test control
System is easier to obtain ideal photochemical catalyst, and improves active carbon to the adsorptivity of nitrogen oxide in tail gas by pretreatment.
The Titanium dioxide/active carbon of the iron of preparation of the invention, nitrogen, cobalt codope, titanium dioxide are evenly arranged on active carbon hole
In gap and surface, titanium dioxide granule is under 100nm, uniform in size；Iron, nitrogen, cobalt doped mention in titanium dioxide lattice
Its high optical property.
The iron of preparation of the invention, nitrogen, cobalt codope Titanium dioxide/active carbon as photocatalyst applications, can be very
Absorption-degradation synergistic effect is played greatly, the efficiency with higher single and repeated removal nitrogen oxides.
Detailed description of the invention
Fig. 1 is iron, nitrogen, cobalt codope titanium dioxide/activity Carbon composites and unsupported titanium dioxide prepared by embodiment 2
Active carbon XRD diffraction pattern；
Fig. 2 is iron, nitrogen, cobalt codope titanium dioxide/activity Carbon composites SEM figure prepared by embodiment 2；
Fig. 3 is that the iron, nitrogen, cobalt codope titanium dioxide/activity Carbon composites UV, visible light of embodiment 1-3 preparation are closely red
Outer absorption spectrum.
Specific embodiment
In order to enable those skilled in the art to better understand the solution of the present invention, below in conjunction in the embodiment of the present invention
Attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only
The embodiment of a part of the invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
The model that the present invention protects all should belong in member's every other embodiment obtained without making creative work
It encloses.
It should be noted that description and claims of this specification and term " first " in above-mentioned attached drawing, "
Two " etc. be to be used to distinguish similar objects, without being used to describe a particular order or precedence order.It should be understood that using in this way
Data be interchangeable under appropriate circumstances, so as to the embodiment of the present invention described herein can in addition to illustrating herein or
Sequence other than those of description is implemented.In addition, term " includes " and " having " and their any deformation, it is intended that cover
Cover it is non-exclusive include, for example, the process, method, system, product or equipment for containing a series of steps or units are not necessarily limited to
Step or unit those of is clearly listed, but may include be not clearly listed or for these process, methods, product
Or other step or units that equipment is intrinsic.
Embodiment 1
A kind of iron, nitrogen, cobalt codope titanium dioxide/activity Carbon composites preparation method, the specific steps are as follows:
Step 1: powdered cocoanut active charcoal being placed in the KOH solution that concentration is 10%, impregnated for 24 hours, later using steaming
Distilled water and dehydrated alcohol are cleaned multiple times, and drying is stand-by；Base extraction can be improved selective absorption of the active carbon to nitrogen oxides；
Distilled water can remove excessive KOH and remaining impurity soluble easily in water, and dehydrated alcohol washing can remove remaining part
Organic impurities.Wherein, the tail gas removal rate without KOH processing AC (active carbon) is 39.8%, the AC tail gas after pre-processing
Removal rate is 56.1%.
Step 2: the dehydrated alcohol that volume ratio is 5:1 is mixed evenly with butyl titanate, nitre acid for adjusting pH is added, until
PH is 2, obtains mixed liquor A；
Step 3: three kinds of ferric nitrate, urea and cobalt nitrate dopants being added to mixed liquor A, high-speed stirred is until all molten
Solution, the mass ratio for obtaining mixed liquid B ferric nitrate, urea and cobalt nitrate and butyl titanate is 0.05:0.08:0.07:1；
Step 4: absorbent charcoal carrier prepared by step 1 is placed in culture dish, is drawn mixed liquid B and is added dropwise in active carbon,
Ultrasonic disperse 10min, is subsequently placed in vacuum oven, is vacuum-treated 10min, makes the abundant wetting activity charcoal of solution, born
Loading A, wherein the mass ratio of active carbon and mixed liquor is 1:3；
Step 5: a bearing table, the bottom of the beaker of 1000mL construction easy reaction room: are placed inside the beaker of 1000mL
Portion fills volume ratio as the mixed liquor of 1:1 dehydrated alcohol and deionized water, and the total volume of dehydrated alcohol and deionized water is
100mL, then the culture dish for filling loaded article A is placed on bearing table, finally seals above-mentioned reaction chamber, 30 DEG C at a temperature of
8h is hydrolyzed, loaded article B is obtained；
Step 6: loaded article B being washed using distilled water and dehydrated alcohol, is dried；
Step 7: the loaded article B after drying is ground, be placed in Muffle furnace and carry out temperature reaction, it is then natural
Cooling, the heating rate of Muffle furnace is 5 DEG C/min, and calcination temperature is 350 DEG C, soaking time 2h, obtains iron, nitrogen, cobalt and is co-doped with
Miscellaneous Titanium dioxide/active carbon compound.Wherein, the tail gas removal rate without KOH processing AC is 39.8%, the AC after pre-processing
Tail gas removal rate is 56.1%.
Embodiment 2
A kind of iron, nitrogen, cobalt codope titanium dioxide/activity Carbon composites preparation method, the specific steps are as follows:
Step 1, powdered cocoanut active charcoal is placed in the NaOH solution that concentration is 10% and is impregnated for 24 hours, later using steaming
Distilled water and dehydrated alcohol are cleaned multiple times, and drying is stand-by；
Step 2: the dehydrated alcohol that volume ratio is 5:1 is mixed evenly with butyl titanate, and passes through nitre acid for adjusting pH,
It is 1 to pH, obtains mixed liquor A；
Step 3: three kinds of ferric nitrate, urea and cobalt nitrate dopants being added to mixed liquor A, high-speed stirred is until all molten
Solution, obtains mixed liquid B, wherein ferric nitrate, urea, cobalt nitrate and butyl titanate mass ratio be 0.05:0.08:0.07:1；
Step 4: absorbent charcoal carrier prepared by step 1 is placed in culture dish, is drawn mixed liquid B and is added dropwise in active carbon,
Ultrasonic disperse 10min, is subsequently placed in vacuum oven, is vacuum-treated 30min, obtains loaded article A, wherein active carbon and mixed
The mass ratio for closing liquid B is 1:3；
Step 5: construction easy reaction room: placing bearing table in the beaker of 1000mL, the beaker bottom of 1000mL fills body
Product compares the mixed liquor for the dehydrated alcohol of 1:1 and the 100mL of deionized water, then the culture dish for filling loaded article A is placed in and holds object
On platform, finally above-mentioned reaction chamber is sealed, in 30 DEG C of hydrolysis 12h, obtains loaded article B；
Step 6: the product of step 7 being washed using distilled water and dehydrated alcohol, is dried；
Step 7: the loaded article B after drying is ground, be placed in Muffle furnace and carry out temperature reaction, it is then natural
Cooling, heating rate is 5 DEG C/min, and calcination temperature is 350 DEG C, soaking time 2h, obtains iron, nitrogen, cobalt codope titanium dioxide
Titanium/activity Carbon composites.
Embodiment 3
A kind of iron, nitrogen, cobalt codope titanium dioxide/activity Carbon composites preparation method, the specific steps are as follows:
Step 1, after powdered cocoanut active charcoal being impregnated for 24 hours in the KOH solution that concentration is 10%, using distilled water and
Dehydrated alcohol is cleaned multiple times, and drying is stand-by；
Step 2: by dehydrated alcohol and butyl titanate that volume ratio is 5:1 according to being mixed evenly, and passing through sulfuric acid tune
PH is saved, until pH is 1.5, obtains mixture A；
Step 3: three kinds of ferric nitrate, urea and cobalt nitrate dopants being added to mixed liquor A, high-speed stirred is until all molten
Solution, obtains mixed liquid B, wherein ferric nitrate, urea, cobalt nitrate and butyl titanate mass ratio be 0.05:0.08:0.07:1；
Step 4: step 1 being prepared into absorbent charcoal carrier and is placed in culture dish, mixed liquid B is drawn and is added dropwise in active carbon, surpass
Sound disperse 10min, be subsequently placed in vacuum oven, be vacuum-treated 45min, obtain loaded article A, wherein active carbon with mix
The mass ratio of liquid B is 1:3；
Step 5: a bearing table, the bottom of the beaker of 1000mL construction easy reaction room: are placed inside the beaker of 1000mL
Portion fills the mixed liquor of the dehydrated alcohol that volume ratio is 1:3 and deionized water, mixeding liquid volume 100mL, then will fill load
The culture dish of object A is placed on bearing table, finally seals above-mentioned reaction chamber, hydrolyzes 12h at 30 DEG C, obtains loaded article B；
Step 6: loaded article B being washed using distilled water and dehydrated alcohol, is dried；
Step 7: the loaded article B after drying is ground, be placed in Muffle furnace and carry out temperature reaction, it is then natural
Cooling, heating rate is 5 DEG C/min, and calcination temperature is 350 DEG C, soaking time 2h, obtains iron, nitrogen, cobalt codope titanium dioxide
Titanium/activity Carbon composites.
Embodiment 4
A kind of iron, nitrogen, cobalt codope titanium dioxide/activity Carbon composites preparation method, the specific steps are as follows:
Step 1, after powdered cocoanut active charcoal being impregnated for 24 hours in the KOH solution that concentration is 3%, using distilled water and
Dehydrated alcohol is cleaned multiple times, and drying is stand-by；
Step 2: by dehydrated alcohol and butyl titanate that volume ratio is 4:1 according to being mixed evenly, and passing through sulfuric acid tune
PH is saved, until pH is 2, obtains mixed liquor A；
Step 3: three kinds of ferric nitrate, urea and cobalt nitrate dopants being added to mixed liquor A, high-speed stirred is until all molten
Solution, obtains mixed liquid B, wherein ferric nitrate, urea, cobalt nitrate and butyl titanate mass ratio be 0.04:0.06:0.05:1；
Step 4: step 1 being prepared into absorbent charcoal carrier and is placed in culture dish, mixed liquid B is drawn and is added dropwise in active carbon, surpass
Sound disperse 10min, be subsequently placed in vacuum oven, be vacuum-treated 60min, obtain loaded article A, wherein active carbon with mix
The mass ratio of liquid B is 1:3；
Step 5: a bearing table, the bottom of the beaker of 1000mL construction easy reaction room: are placed inside the beaker of 1000mL
Portion fills the mixed liquor of the dehydrated alcohol that volume ratio is 1:2 and deionized water, then the culture dish for filling loaded article A is placed in and holds object
On platform, finally above-mentioned reaction chamber is sealed, hydrolyzes 11h at 30 DEG C, obtains loaded article B；
Step 6: loaded article B being washed using distilled water and dehydrated alcohol, is dried；
Step 7: the loaded article B after drying is ground, be placed in Muffle furnace and carry out temperature reaction, it is then natural
Cooling, heating rate is 10 DEG C/min, and calcination temperature is 250 DEG C, soaking time 1.5h, obtains iron, nitrogen, cobalt codope dioxy
Change titanium/activity Carbon composites.
Embodiment 5
A kind of iron, nitrogen, cobalt codope titanium dioxide/activity Carbon composites preparation method, the specific steps are as follows:
Step 1: after powdered cocoanut active charcoal is impregnated for 24 hours in the KOH solution that concentration is 3%, using distilled water and
Dehydrated alcohol is cleaned multiple times, and drying is stand-by；
Step 2: by dehydrated alcohol and butyl titanate that volume ratio is 5:1 according to being mixed evenly, and passing through sulfuric acid tune
PH is saved, until pH is 1.5, obtains mixed liquor A；
Step 3: three kinds of ferric nitrate, urea and cobalt nitrate dopants being added to mixed liquor A, high-speed stirred is until all molten
Solution, obtains mixed liquid B, ferric nitrate, urea, cobalt nitrate and butyl titanate mass ratio be 0.05:0.08:0.07:1；
Step 4: step 1 being prepared into absorbent charcoal carrier and is placed in culture dish, mixed liquid B is drawn and is added dropwise in active carbon, surpass
Sound disperse 10min, be subsequently placed in vacuum oven, be vacuum-treated 30min, obtain loaded article A, wherein active carbon with mix
The mass ratio of liquid B is 1:3；
Step 5: a bearing table, the bottom of the beaker of 1000mL construction easy reaction room: are placed inside the beaker of 1000mL
Portion fills the mixed liquor of the dehydrated alcohol that volume ratio is 1:2 and deionized water, then will fill loaded article A and be placed on bearing table, most
Above-mentioned reaction chamber is sealed afterwards, hydrolyzes 12h at 30 DEG C, obtains loaded article B；
Step 6: loaded article B being washed using distilled water and dehydrated alcohol, is dried；
Step 7: the loaded article B after drying is ground, be placed in Muffle furnace and carry out temperature reaction, it is then natural
Cooling, heating rate is 5 DEG C/min, and calcination temperature is 350 DEG C, soaking time 2h, obtains iron, nitrogen, cobalt codope titanium dioxide
Titanium/activity Carbon composites.
Embodiment 6
A kind of iron, nitrogen, cobalt codope titanium dioxide/activity Carbon composites preparation method, the specific steps are as follows:
Step 1, after powdered cocoanut active charcoal being impregnated for 24 hours in the KOH solution that concentration is 3%, using distilled water and
Dehydrated alcohol is cleaned multiple times, and drying is stand-by；
Step 2: by dehydrated alcohol and butyl titanate that volume ratio is 4.5:1 according to being mixed evenly, and passing through sulfuric acid
PH is adjusted, until pH is 1.5, obtains mixed liquor A；
Step 3: three kinds of ferric nitrate, urea and cobalt nitrate dopants being added to mixed liquor A, high-speed stirred is until all molten
Solution, obtains mixed liquid B, wherein ferric nitrate, urea, cobalt nitrate and butyl titanate mass ratio be 0.06:0.10:0.09:1；
Step 4: step 1 being prepared into absorbent charcoal carrier and is placed in culture dish, mixed liquid B is drawn and is added dropwise in active carbon, so
Postposition in a vacuum drying oven, is vacuum-treated 60min, makes the abundant wetting activity charcoal of solution, obtain loaded article A, wherein active carbon
Mass ratio with mixed liquid B is 1:3；
Step 5: a bearing table, the bottom of the beaker of 1000mL construction easy reaction room: are placed inside the beaker of 1000mL
Portion fills the mixed liquor of the 100mL of the dehydrated alcohol that volume ratio is 1:2 and deionized water, then the culture dish that will fill loaded article A
It is placed on bearing table, finally seals above-mentioned reaction chamber, hydrolyze 11h at 30 DEG C, obtain loaded article B；
Step 6: loaded article B being washed using distilled water and dehydrated alcohol, is dried；
Step 7: the loaded article B after drying is ground, be placed in Muffle furnace and carry out temperature reaction, it is then natural
Cooling, heating rate is 10 DEG C/min, and calcination temperature is 300 DEG C, soaking time 1h, obtains iron, nitrogen, cobalt codope titanium dioxide
Titanium/activity Carbon composites.
Table 1 is iron, nitrogen, cobalt codope titanium dioxide/active carbon complex degradation methylene blue and the nitrogen oxygen of embodiment 1-3
The degradation data of compound, it can be seen that the degradation efficiency highest of 2 methylene blue of embodiment and nitrogen oxides Degrading experiment, preferably
The synergistic effect of absorption and degradation is played；And embodiment 1, since hydrolysis time is shorter, the load capacity of photochemical catalyst is smaller, and
Crystal form is not perfect, therefore its degradation effect is poor, predominantly adsorption effect；3 hydrolysis rate of embodiment is fast, and hydrolysis time is longer,
The particle of the modifying titanium dioxide of formation is coarseer, largely affects the hole of photocatalytic activity (degradation) and active carbon
Road structure (suction-operated).
Iron, nitrogen, cobalt codope titanium dioxide/active carbon complex degradation methylene blue and the nitrogen oxidation of 1 embodiment 1-3 of table
The degradation data of object
The invention will be described in further detail with reference to the accompanying drawing:
Referring to Fig. 1, Fig. 1 be embodiment 2 prepare iron, nitrogen, cobalt codope titanium dioxide/activity Carbon composites with it is unsupported
The XRD diffraction pattern of the active carbon of titanium dioxide；As seen from the figure, the active carbon for having loaded titanium dioxide has the diffraction of Detitanium-ore-type
Peak (25.3 °, irised out in figure), and the part diffraction peak intensity of active carbon is weakened, and illustrates that titanium dioxide has been carried on work
Inside property charcoal, and have a certain impact to the cellular structure of active carbon.
Referring to fig. 2, Fig. 2 is iron, nitrogen, cobalt codope titanium dioxide/activity Carbon composites SEM figure prepared by embodiment 2,
As seen from the figure, photochemical catalyst is grown to fine particle on the activated carbon, and granular size is tens to one hundred nanometer.In conjunction with XRD diagram
Spectrum is analyzed, and the modifying titanium dioxide particle on surface is reunited, but non-aggregated is micron particles, and to the hole of active carbon
Road structure influences less.
Referring to Fig. 3, Fig. 3 is that the iron, nitrogen, cobalt codope titanium dioxide/activity Carbon composites of embodiment 1-3 preparation are ultraviolet
Visible near-infrared absorption spectrum；As seen from the figure, the optical absorption intensity highest of case study on implementation 2 illustrates by controlling its hydrolysis rate
The crystal form and grain size of the photochemical catalyst of acquisition are optimal；Photochemical catalyst in embodiment 1 may hydrolyze not exclusively, and the two of formation
Titanium oxide crystal form is incomplete, and has element dopants not fully doped into titanium dioxide, and ferrotianium is formed in calcination process
Mine causes its UV Absorption intensity lower, it is seen that light absorption increased that (forbidden bandwidth of arizonite is than titanium dioxide
It is small)；Hydrolysis rate in embodiment 3 is too fast, and the crystal grain for causing titanium dioxide to be formed is larger, influences photocatalytic activity.
The above content is merely illustrative of the invention's technical idea, and this does not limit the scope of protection of the present invention, all to press
According to technical idea proposed by the present invention, any changes made on the basis of the technical scheme each falls within claims of the present invention
Protection scope within.
Claims (8)
1. a kind of preparation method of the Titanium dioxide/active carbon compound of iron, nitrogen, cobalt codope, which is characterized in that including following
Step:
1) butyl titanate is dissolved in dehydrated alcohol, adjusting pH is 1-2, obtains mixed liquor A；Wherein, butyl titanate and anhydrous second
The volume ratio of alcohol is 1:(4-5)；
2) ferric nitrate, urea and cobalt nitrate are dissolved in mixed liquor A, obtain mixed liquid B；Wherein, ferric nitrate, urea, cobalt nitrate
Mass ratio with butyl titanate is (0.04-0.06): (0.06-0.10): (0.05-0.09): 1；
3) it disperses mixed liquid B in active carbon, obtains loaded article A；
4) loaded article A is placed in the atmosphere of water vapour and dehydrated alcohol steam, butyl titanate hydrolyzes, and obtains loaded article B；
Wherein, the atmosphere of the water vapour and dehydrated alcohol steam is provided by the water and dehydrated alcohol being placed in confined space, anhydrous second
The volume ratio of alcohol and water is 1:(1-3)；
5) it by after loaded article B washing, drying, grinding, is placed at 250-350 DEG C and calcines 1-2h, obtain iron, nitrogen, cobalt codope
Titanium dioxide/active carbon compound.
2. the preparation method of the Titanium dioxide/active carbon compound of iron according to claim 1, nitrogen, cobalt codope, special
Sign is that the active carbon in step 3) is the cocoanut active charcoal by base extraction.
3. the preparation method of the Titanium dioxide/active carbon compound of iron according to claim 1, nitrogen, cobalt codope, special
Sign is that the mass ratio of the mixed liquid B and active carbon that are dispersed in active carbon in step 3) is 3:1.
4. the preparation method of the Titanium dioxide/active carbon compound of iron according to claim 1, nitrogen, cobalt codope, special
Sign is, disperses mixed liquid B in active carbon in step 3), and 10-60min is placed in subnormal ambient, obtains loaded article A.
5. the preparation method of the Titanium dioxide/active carbon compound of iron according to claim 4, nitrogen, cobalt codope, special
Sign is that the temperature that butyl titanate hydrolyzes is 30 DEG C, hydrolysis time 8-12h.
6. the preparation method of the Titanium dioxide/active carbon compound of iron according to claim 1, nitrogen, cobalt codope, special
Sign is that the ratio between volume of total volume and confined space of dehydrated alcohol and water is 1:10 in step 4).
7. the Titanium dioxide/active carbon compound of a kind of iron according to claim 1-6, nitrogen, cobalt codope
Iron that preparation method is prepared, nitrogen, cobalt codope Titanium dioxide/active carbon compound.
8. the Titanium dioxide/active carbon compound of iron according to claim 7, nitrogen, cobalt codope, which is characterized in that make
For the application of photochemical catalyst catalytic degradation nitrogen oxides.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114146722A (en) * | 2021-12-13 | 2022-03-08 | 河北建设集团股份有限公司 | Method for degrading sulfamethoxazole by using wood sponge in cooperation with thermal activation of persulfate |
| CN115055188A (en) * | 2022-06-10 | 2022-09-16 | 长安大学 | Composite modified nano TiO for tunnel 2 Tail gas degradation material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101036878A (en) * | 2007-04-06 | 2007-09-19 | 武汉理工大学 | Steam heat method for preparing high-crystallized nanocrystalline titanium dioxide photocatalyst |
| CN104907089A (en) * | 2015-05-29 | 2015-09-16 | 西安科技大学 | A preparation method of N, fe, zn-TiO2/AC photocatalyst |
| CN105597718A (en) * | 2015-10-12 | 2016-05-25 | 福建师范大学泉港石化研究院 | Preparation method of inorganic mineral powder supported nano-TiO2 photocatalyst |
| CN105618053A (en) * | 2016-02-25 | 2016-06-01 | 济南大学 | Preparation method of double-metal doped titanium dioxide polyhedral photocatalyst |
| CN108884339A (en) * | 2015-11-20 | 2018-11-23 | 维纳特材料英国有限公司 | coating |
-
2019
- 2019-06-25 CN CN201910557377.XA patent/CN110252375B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101036878A (en) * | 2007-04-06 | 2007-09-19 | 武汉理工大学 | Steam heat method for preparing high-crystallized nanocrystalline titanium dioxide photocatalyst |
| CN104907089A (en) * | 2015-05-29 | 2015-09-16 | 西安科技大学 | A preparation method of N, fe, zn-TiO2/AC photocatalyst |
| CN105597718A (en) * | 2015-10-12 | 2016-05-25 | 福建师范大学泉港石化研究院 | Preparation method of inorganic mineral powder supported nano-TiO2 photocatalyst |
| CN108884339A (en) * | 2015-11-20 | 2018-11-23 | 维纳特材料英国有限公司 | coating |
| CN105618053A (en) * | 2016-02-25 | 2016-06-01 | 济南大学 | Preparation method of double-metal doped titanium dioxide polyhedral photocatalyst |
Non-Patent Citations (1)
| Title |
|---|
| 上海交通大学主编: "《机电词典》", 31 October 1991 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114146722A (en) * | 2021-12-13 | 2022-03-08 | 河北建设集团股份有限公司 | Method for degrading sulfamethoxazole by using wood sponge in cooperation with thermal activation of persulfate |
| CN114146722B (en) * | 2021-12-13 | 2023-08-08 | 河北建设集团股份有限公司 | Method for degrading sulfamethoxazole by wood sponge synergistic heat activation persulfate |
| CN115055188A (en) * | 2022-06-10 | 2022-09-16 | 长安大学 | Composite modified nano TiO for tunnel 2 Tail gas degradation material and preparation method thereof |
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