CN110252375B - A kind of iron, nitrogen, cobalt co-doped titanium dioxide/activated carbon composite, preparation method and application as photocatalyst - Google Patents
A kind of iron, nitrogen, cobalt co-doped titanium dioxide/activated carbon composite, preparation method and application as photocatalyst Download PDFInfo
- Publication number
- CN110252375B CN110252375B CN201910557377.XA CN201910557377A CN110252375B CN 110252375 B CN110252375 B CN 110252375B CN 201910557377 A CN201910557377 A CN 201910557377A CN 110252375 B CN110252375 B CN 110252375B
- Authority
- CN
- China
- Prior art keywords
- activated carbon
- titanium dioxide
- cobalt
- nitrogen
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 243
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 139
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 90
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 66
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 45
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 44
- 239000010941 cobalt Substances 0.000 title claims abstract description 44
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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 Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 17
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 17
- 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 24
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 18
- 244000060011 Cocos nucifera Species 0.000 claims description 18
- 238000006731 degradation reaction Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 230000015556 catabolic process Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000012153 distilled water Substances 0.000 description 13
- 239000002019 doping agent Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 230000003301 hydrolyzing effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000009489 vacuum treatment Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 230000002195 synergetic effect Effects 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
- 239000003054 catalyst Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000001027 hydrothermal synthesis 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
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound, a preparation method and application thereof as a photocatalyst, and belongs to the field of titanium dioxide compounding. A preparation method of an iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon composite comprises the following steps: 1) dissolving butyl titanate in absolute ethyl alcohol to obtain a mixed solution A; 2) dissolving ferric nitrate, urea and cobalt nitrate in the mixed solution A to obtain a mixed solution B; 3) dispersing the mixed solution B in the activated carbon to obtain a load A; 4) putting the load A in the atmosphere of water vapor and absolute ethyl alcohol vapor to obtain a load B; 5) and calcining the load B to obtain the iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon composite. The preparation method controls the molding of titanium dioxide on the active carbon and the particle size by controlling the hydrolysis speed of titanate, and obtains an ideal photocatalyst.
Description
Technical Field
The invention belongs to the field of titanium dioxide compounding, and particularly relates to an iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound, a preparation method and application thereof as a photocatalyst.
Background
With the increasing automobile holding capacity, the problem of exhaust pollution needs to be solved urgently. Therefore, the photocatalyst titanium dioxide is favored in the field of tail gas purification due to the characteristics of high catalytic activity, chemical stability and no toxicity and harm. Therefore, people develop a photocatalytic degradation tail gas material, wherein the photocatalytic coating loaded with nano titanium dioxide belongs to one of the materials, the nano titanium dioxide is used as a photocatalyst and can catalyze and oxidize most pollutants in the air, and degradation products are nontoxic and harmless micromolecular substances.
At present, the existing photocatalysis tail gas purification treatment means are adopted, but the requirements on light sources are higher, and the degradation efficiency and the catalyst utilization rate are lower. When the photocatalyst is used for degrading air pollutants, the active site of the catalyst is required to be in effective contact with the pollutants, the surface of the nano titanium dioxide is high in surface energy and easy to agglomerate, the contact area of the active site and the pollutants is reduced, and the degradation efficiency is greatly influenced. The catalyst is loaded by using the porous material-active carbon as a carrier, so that not only can the agglomeration of the nano titanium dioxide be prevented, but also an adsorption-degradation synergistic effect can be formed, and the removal efficiency is further improved. The existing methods for preparing the modified titanium dioxide-doped active carbon composite photocatalyst mainly comprise a ball milling method, a sol-gel method and a hydrothermal method. Wherein the loading capacity of the modified titanium dioxide and the hydrolysis speed in the preparation process are not easy to control, and the prepared composite photocatalyst is difficult to exert the adsorption-degradation synergistic effect. For example, patent CN108786732 adopts a sol-gel method to prepare a titanium dioxide/biomass activated carbon composite photocatalyst, which does not modify titanium dioxide, and has a high degradation efficiency only under ultraviolet irradiation, but has a low degradation efficiency under visible light, a low light source utilization rate, and a limited application range. The iron and nitrogen co-doped titanium dioxide/activated carbon photocatalyst prepared in patent CN103240110 adopts a sol impregnation preparation method, the hydrolysis speed of titanium dioxide in the preparation process is difficult to control, and the sol impregnation easily causes the spontaneous hydrolysis of excess sol to form free titanium dioxide particles, so that the activated carbon is incompletely loaded.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon composite, a preparation method and application thereof as a photocatalyst.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of an iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon composite comprises the following steps:
1) dissolving butyl titanate in absolute ethyl alcohol, and adjusting the pH value to 1-2 to obtain a mixed solution A; wherein the volume ratio of the butyl titanate to the absolute ethyl alcohol is 1: (4-5);
2) dissolving ferric nitrate, urea and cobalt nitrate in the mixed solution A to obtain a mixed solution B; wherein the mass ratio of the ferric nitrate to the urea to the cobalt nitrate to the butyl titanate is (0.04-0.06): (0.06-0.10): (0.05-0.09): 1;
3) dispersing the mixed solution B in the activated carbon to obtain a load A;
4) placing the load A in the atmosphere of water vapor and absolute ethyl alcohol vapor, and hydrolyzing butyl titanate to obtain a load B; wherein, the atmosphere of the water vapor and the absolute ethyl alcohol vapor is provided by water and absolute ethyl alcohol which are arranged in the closed space, and the volume ratio of the absolute ethyl alcohol to the water is 1: (1-3);
5) and (3) washing, drying and grinding the load B, and calcining for 1-2h at the temperature of 250-350 ℃ to obtain the iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon composite.
Further, the activated carbon in the step 3) is coconut shell activated carbon treated by alkali liquor.
Further, the mass ratio of the mixed solution B dispersed in the activated carbon in the step 3) to the activated carbon is 3: 1.
further, dispersing the mixed solution B in the activated carbon in the step 3), and standing for 10-60min in a negative pressure environment to obtain the load A.
Furthermore, the temperature for hydrolyzing the butyl titanate is 30 ℃, and the hydrolysis time is 8-12 h.
Further, the ratio of the total volume of the absolute ethyl alcohol and the water in the step 4) to the volume of the closed space is 1: 10.
An iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon composite prepared by the preparation method.
Further, the photocatalyst is used for catalyzing and degrading nitrogen oxides.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound, the traditional sol-gel method for preparing titanium dioxide is improved, the titanium dioxide prepared by the traditional sol-gel method is large in particle size, the crystal form can be controlled only by the calcination temperature, and the calcination temperature cannot be too high when the activated carbon is used as a carrier, so that the adsorption strength of the activated carbon is influenced; when the calcination temperature is lower, the crystal form of the titanium dioxide is imperfect, and the catalytic effect of the titanium dioxide is influenced. The method controls the molding and particle size of titanium dioxide on the activated carbon by controlling the hydrolysis speed of titanate, avoids the single-factor control of crystal form by calcination temperature, is easier to obtain an ideal photocatalyst, and improves the adsorbability of the activated carbon to nitrogen oxides in tail gas by pretreatment.
According to the iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon prepared by the method, titanium dioxide is uniformly distributed in pores and on the surface of the activated carbon, and titanium dioxide particles are below 100nm and are uniform in size; the iron, nitrogen and cobalt are doped in the titanium dioxide crystal lattice, so that the optical performance of the titanium dioxide crystal lattice is improved.
The iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon prepared by the method disclosed by the invention is applied as a photocatalyst, can greatly exert the synergistic effect of adsorption and degradation, and has higher efficiency of removing nitrogen oxides once and repeatedly.
Drawings
FIG. 1 is an XRD diffractogram of the iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon composite prepared in example 2 and the activated carbon without supported titanium dioxide;
FIG. 2 is an SEM image of an iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon composite prepared in example 2;
fig. 3 is an ultraviolet-visible near-infrared absorption spectrum of the iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon composite prepared in examples 1-3.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1
A preparation method of an iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound comprises the following specific steps:
step 1: putting powdered coconut shell activated carbon into 10% KOH solution, soaking for 24h, then washing for many times by using distilled water and absolute ethyl alcohol, and drying for later use; the selective adsorption of the active carbon to the nitrogen oxides can be improved by alkali liquor treatment; the excessive KOH and the rest impurities which are easy to dissolve in water can be removed by distilled water, and the residual organic impurities can be removed by washing with absolute ethyl alcohol. Wherein, the tail gas removal rate of the AC (activated carbon) without KOH treatment is 39.8%, and the AC tail gas removal rate after pretreatment is 56.1%.
Step 2: mixing absolute ethyl alcohol and butyl titanate with the volume ratio of 5:1, uniformly stirring, adding nitric acid to adjust the pH value to 2, and obtaining a mixed solution A;
and step 3: adding three doping agents of ferric nitrate, urea and cobalt nitrate into the mixed solution A, stirring at a high speed until the three doping agents are completely dissolved, and obtaining a mixed solution B, wherein the mass ratio of the ferric nitrate to the urea to the cobalt nitrate to the butyl titanate is 0.05: 0.08: 0.07: 1;
and 4, step 4: placing the activated carbon carrier prepared in the step 1 in a culture dish, sucking the mixed solution B and dropwise adding the mixed solution B into the activated carbon, ultrasonically dispersing for 10min, then placing the activated carbon carrier in a vacuum drying oven, and carrying out vacuum treatment for 10min to ensure that the solution fully wets the activated carbon to obtain a load A, wherein the mass ratio of the activated carbon to the mixed solution is 1: 3;
and 5: the structure of the simple reaction chamber is as follows: placing a bearing platform in a 1000mL beaker, placing a mixed solution of absolute ethyl alcohol and deionized water with the volume ratio of 1:1 at the bottom of the 1000mL beaker, wherein the total volume of the absolute ethyl alcohol and the deionized water is 100mL, placing a culture dish containing a load A on the bearing platform, sealing the reaction chamber, and hydrolyzing at 30 ℃ for 8 hours to obtain a load B;
step 6: washing and drying the load B by using distilled water and absolute ethyl alcohol;
and 7: and grinding the dried load B, then placing the load B in a muffle furnace for heating reaction, and then naturally cooling the load B, wherein the heating speed of the muffle furnace is 5 ℃/min, the calcining temperature is 350 ℃, and the heat preservation time is 2h, so that the iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound is obtained. Wherein, the removal rate of the tail gas of the AC without KOH treatment is 39.8 percent, and the removal rate of the AC tail gas after pretreatment is 56.1 percent.
Example 2
A preparation method of an iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound comprises the following specific steps:
step 1, soaking powdered coconut shell activated carbon in a 10% NaOH solution for 24 hours, then washing the powdered coconut shell activated carbon for multiple times by using distilled water and absolute ethyl alcohol, and drying the coconut shell activated carbon for later use;
step 2: mixing absolute ethyl alcohol and butyl titanate with the volume ratio of 5:1, uniformly stirring, and adjusting the pH value to 1 by nitric acid to obtain a mixed solution A;
and step 3: adding three doping agents of ferric nitrate, urea and cobalt nitrate into the mixed solution A, and stirring at a high speed until the doping agents are completely dissolved to obtain a mixed solution B, wherein the mass ratio of the ferric nitrate to the urea to the cobalt nitrate to the butyl titanate is 0.05: 0.08: 0.07: 1;
and 4, step 4: placing the activated carbon carrier prepared in the step 1 in a culture dish, sucking the mixed solution B and dripping the mixed solution B into the activated carbon, ultrasonically dispersing for 10min, then placing the activated carbon carrier in a vacuum drying oven, and performing vacuum treatment for 30min to obtain a load A, wherein the mass ratio of the activated carbon to the mixed solution B is 1: 3;
and 5: the structure of the simple reaction chamber is as follows: placing a bearing platform in a 1000mL beaker, wherein the bottom of the 1000mL beaker is filled with a mixture of the materials with the volume ratio of 1:1, placing a culture dish containing a load A on a bearing platform, sealing the reaction chamber, and hydrolyzing at 30 ℃ for 12 hours to obtain a load B;
step 6: washing and drying the product obtained in the step 7 by using distilled water and absolute ethyl alcohol;
and 7: and grinding the dried load B, then placing the load B in a muffle furnace for heating reaction, and then naturally cooling the load B, wherein the heating speed is 5 ℃/min, the calcining temperature is 350 ℃, and the heat preservation time is 2h, so that the iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound is obtained.
Example 3
A preparation method of an iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound comprises the following specific steps:
step 1, soaking powdered coconut shell activated carbon in a KOH solution with the concentration of 10% for 24 hours, washing the powdered coconut shell activated carbon for multiple times by using distilled water and absolute ethyl alcohol, and drying the powdered coconut shell activated carbon for later use;
step 2: mixing absolute ethyl alcohol and butyl titanate according to the volume ratio of 5:1, uniformly stirring, and adjusting the pH value to 1.5 by using sulfuric acid to obtain a mixture A;
and step 3: adding three doping agents of ferric nitrate, urea and cobalt nitrate into the mixed solution A, and stirring at a high speed until the doping agents are completely dissolved to obtain a mixed solution B, wherein the mass ratio of the ferric nitrate to the urea to the cobalt nitrate to the butyl titanate is 0.05: 0.08: 0.07: 1;
and 4, step 4: placing the activated carbon carrier prepared in the step 1 in a culture dish, sucking the mixed solution B and dripping the mixed solution B in the activated carbon, ultrasonically dispersing for 10min, then placing the activated carbon carrier in a vacuum drying oven, and performing vacuum treatment for 45min to obtain a load A, wherein the mass ratio of the activated carbon to the mixed solution B is 1: 3;
and 5: the structure of the simple reaction chamber is as follows: placing a bearing platform in a 1000mL beaker, wherein the bottom of the 1000mL beaker is filled with a mixed solution of absolute ethyl alcohol and deionized water in a volume ratio of 1:3, the volume of the mixed solution is 100mL, placing a culture dish containing a load A on the bearing platform, sealing the reaction chamber, and hydrolyzing at 30 ℃ for 12 hours to obtain a load B;
step 6: washing and drying the load B by using distilled water and absolute ethyl alcohol;
and 7: and grinding the dried load B, then placing the load B in a muffle furnace for heating reaction, and then naturally cooling the load B, wherein the heating speed is 5 ℃/min, the calcining temperature is 350 ℃, and the heat preservation time is 2h, so that the iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound is obtained.
Example 4
A preparation method of an iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound comprises the following specific steps:
step 1, soaking powdered coconut shell activated carbon in a KOH solution with the concentration of 3% for 24 hours, washing the powdered coconut shell activated carbon for multiple times by using distilled water and absolute ethyl alcohol, and drying the powdered coconut shell activated carbon for later use;
step 2: mixing absolute ethyl alcohol and butyl titanate according to a volume ratio of 4:1, uniformly stirring, and adjusting the pH value to 2 by using sulfuric acid to obtain a mixed solution A;
and step 3: adding three doping agents of ferric nitrate, urea and cobalt nitrate into the mixed solution A, and stirring at a high speed until the doping agents are completely dissolved to obtain a mixed solution B, wherein the mass ratio of the ferric nitrate to the urea to the cobalt nitrate to the butyl titanate is 0.04: 0.06: 0.05: 1;
and 4, step 4: placing the activated carbon carrier prepared in the step 1 in a culture dish, sucking the mixed solution B and dripping the mixed solution B into the activated carbon, ultrasonically dispersing for 10min, then placing the activated carbon carrier in a vacuum drying oven, and performing vacuum treatment for 60min to obtain a load A, wherein the mass ratio of the activated carbon to the mixed solution B is 1: 3;
and 5: the structure of the simple reaction chamber is as follows: a bearing platform is arranged in a 1000mL beaker, and the bottom of the 1000mL beaker is filled with a material with the volume ratio of 1: 2, placing a culture dish containing the load A on a bearing platform, sealing the reaction chamber, and hydrolyzing at 30 ℃ for 11 hours to obtain a load B;
step 6: washing and drying the load B by using distilled water and absolute ethyl alcohol;
and 7: and grinding the dried load B, then placing the load B in a muffle furnace for heating reaction, and then naturally cooling the load B, wherein the heating speed is 10 ℃/min, the calcining temperature is 250 ℃, and the heat preservation time is 1.5h, so that the iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound is obtained.
Example 5
A preparation method of an iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound comprises the following specific steps:
step 1: soaking powdered coconut shell activated carbon in a KOH solution with the concentration of 3% for 24 hours, washing the powdered coconut shell activated carbon for multiple times by using distilled water and absolute ethyl alcohol, and drying the powdered coconut shell activated carbon for later use;
step 2: mixing absolute ethyl alcohol and butyl titanate according to the volume ratio of 5:1, uniformly stirring, and adjusting the pH value to 1.5 by using sulfuric acid to obtain a mixed solution A;
and step 3: adding three doping agents of ferric nitrate, urea and cobalt nitrate into the mixed solution A, stirring at a high speed until the doping agents are completely dissolved to obtain a mixed solution B, wherein the mass ratio of the ferric nitrate to the urea to the cobalt nitrate to the butyl titanate is 0.05: 0.08: 0.07: 1;
and 4, step 4: placing the activated carbon carrier prepared in the step 1 in a culture dish, sucking the mixed solution B and dripping the mixed solution B in the activated carbon, ultrasonically dispersing for 10min, then placing the activated carbon carrier in a vacuum drying oven, and performing vacuum treatment for 30min to obtain a load A, wherein the mass ratio of the activated carbon to the mixed solution B is 1: 3;
and 5: the structure of the simple reaction chamber is as follows: a bearing platform is arranged in a 1000mL beaker, and the bottom of the 1000mL beaker is filled with a material with the volume ratio of 1: 2, placing the load A on a bearing platform, sealing the reaction chamber, and hydrolyzing at 30 ℃ for 12 hours to obtain a load B;
step 6: washing and drying the load B by using distilled water and absolute ethyl alcohol;
and 7: and grinding the dried load B, then placing the load B in a muffle furnace for heating reaction, and then naturally cooling the load B, wherein the heating speed is 5 ℃/min, the calcining temperature is 350 ℃, and the heat preservation time is 2h, so that the iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound is obtained.
Example 6
A preparation method of an iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound comprises the following specific steps:
step 1, soaking powdered coconut shell activated carbon in a KOH solution with the concentration of 3% for 24 hours, washing the powdered coconut shell activated carbon for multiple times by using distilled water and absolute ethyl alcohol, and drying the powdered coconut shell activated carbon for later use;
step 2: mixing the components in a volume ratio of 4.5: 1, uniformly mixing and stirring the absolute ethyl alcohol and butyl titanate, and adjusting the pH value to 1.5 by using sulfuric acid to obtain a mixed solution A;
and step 3: adding three doping agents of ferric nitrate, urea and cobalt nitrate into the mixed solution A, and stirring at a high speed until the doping agents are completely dissolved to obtain a mixed solution B, wherein the mass ratio of the ferric nitrate to the urea to the cobalt nitrate to the butyl titanate is 0.06: 0.10: 0.09: 1;
and 4, step 4: placing the activated carbon carrier prepared in the step 1 in a culture dish, sucking the mixed solution B and dripping the mixed solution B into the activated carbon, then placing the activated carbon in a vacuum drying oven, and carrying out vacuum treatment for 60min to ensure that the solution fully wets the activated carbon to obtain a load A, wherein the mass ratio of the activated carbon to the mixed solution B is 1: 3;
and 5: the structure of the simple reaction chamber is as follows: a bearing platform is arranged in a 1000mL beaker, and the bottom of the 1000mL beaker is filled with a material with the volume ratio of 1: 2, placing a culture dish containing the load A on a bearing platform, sealing the reaction chamber, and hydrolyzing for 11 hours at 30 ℃ to obtain a load B;
step 6: washing and drying the load B by using distilled water and absolute ethyl alcohol;
and 7: and grinding the dried load B, then placing the load B in a muffle furnace for heating reaction, and then naturally cooling the load B, wherein the heating speed is 10 ℃/min, the calcining temperature is 300 ℃, and the heat preservation time is 1h, so that the iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon compound is obtained.
Table 1 shows the degradation data of the iron, nitrogen, and cobalt co-doped titanium dioxide/activated carbon composite in examples 1 to 3 for degrading methylene blue and nitrogen oxide, and it can be seen that the degradation efficiency of the methylene blue and nitrogen oxide degradation test in example 2 is the highest, and the synergistic effect of adsorption and degradation is better exerted; in example 1, the hydrolysis time is short, the loading amount of the photocatalyst is small, and the crystal form is imperfect, so that the degradation effect is poor, mainly the adsorption effect; example 3 hydrolysis speed is high, hydrolysis time is long, particles of the formed modified titanium dioxide are coarse, and photocatalytic activity (degradation) and pore structure (adsorption) of activated carbon are greatly influenced.
TABLE 1 degradation data of the iron, nitrogen, and cobalt co-doped titanium dioxide/activated carbon composites of examples 1-3 for degrading methylene blue and nitrogen oxides
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, fig. 1 is an XRD diffractogram of the iron, nitrogen and cobalt co-doped titania/activated carbon composite prepared in example 2 and the activated carbon not loaded with titania; as can be seen from the figure, the activated carbon loaded with titanium dioxide has an anatase type diffraction peak (25.3 °, circled in the figure), and the intensity of the partial diffraction peak of the activated carbon is reduced, which indicates that titanium dioxide is already loaded in the activated carbon and has a certain effect on the pore structure of the activated carbon.
Referring to fig. 2, fig. 2 is an SEM image of the iron, nitrogen and cobalt co-doped titania/activated carbon composite prepared in example 2, and it can be seen that the photocatalyst grows as fine particles on the activated carbon, and the particle size is several tens to one hundred nanometers. The modified titanium dioxide particles on the surface are agglomerated to some extent but are not agglomerated to micron-sized particles by analyzing with an XRD (X-ray diffraction) pattern, and the influence on the pore structure of the activated carbon is less.
Referring to fig. 3, fig. 3 is an ultraviolet-visible near-infrared absorption spectrum of the iron, nitrogen and cobalt co-doped titanium dioxide/activated carbon composite prepared in examples 1 to 3; as can be seen from the figure, the light absorption intensity of the embodiment 2 is the highest, which shows that the crystal form and the grain size of the photocatalyst obtained by controlling the hydrolysis rate are the best; the photocatalyst in example 1 may be incompletely hydrolyzed, the crystal form of the formed titanium dioxide is not complete, and part of the dopant is not completely doped into the titanium dioxide, and ilmenite is formed in the calcination process, so that the ultraviolet light absorption intensity is low, and the visible light absorption is increased (the forbidden bandwidth of the ilmenite is smaller than that of the titanium dioxide); the hydrolysis rate in example 3 is too fast, resulting in larger grains of titanium dioxide, affecting the photocatalytic activity.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910557377.XA CN110252375B (en) | 2019-06-25 | 2019-06-25 | A kind of iron, nitrogen, cobalt co-doped titanium dioxide/activated carbon composite, preparation method and application as photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910557377.XA CN110252375B (en) | 2019-06-25 | 2019-06-25 | A kind of iron, nitrogen, cobalt co-doped titanium dioxide/activated carbon composite, preparation method and application as photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110252375A CN110252375A (en) | 2019-09-20 |
| CN110252375B true CN110252375B (en) | 2021-06-29 |
Family
ID=67921631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910557377.XA Active CN110252375B (en) | 2019-06-25 | 2019-06-25 | A kind of iron, nitrogen, cobalt co-doped titanium dioxide/activated carbon composite, preparation method and application as photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110252375B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114146722B (en) * | 2021-12-13 | 2023-08-08 | 河北建设集团股份有限公司 | A method of synergistically thermally activating persulfate to degrade sulfamethoxazole with wood sponge |
| 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 kind of 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 layer |
-
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 kind of 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 layer |
| CN105618053A (en) * | 2016-02-25 | 2016-06-01 | 济南大学 | Preparation method of double-metal doped titanium dioxide polyhedral photocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110252375A (en) | 2019-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105642299B (en) | A kind of cadmium ferrite/clay nano structural composite material and its preparation method and application of nickel doping | |
| CN103172030B (en) | Oxide powder and preparation method thereof as well as catalyst and carrier thereof | |
| CN111185152B (en) | A preparation method of multifunctional coupling PAC/Bi2O3/TiO2 composite material | |
| CN106964358A (en) | A kind of cadmium ferrite/concave convex rod nano composite material of carbon quantum dot modification and its preparation method and application | |
| CN102974379B (en) | Method for preparing nitrogen-doped photo-catalytic material containing gallium oxide at low temperature | |
| CN101670282A (en) | Preparation method of load type nano titanium dioxide catalyst | |
| CN110252375B (en) | A kind of iron, nitrogen, cobalt co-doped titanium dioxide/activated carbon composite, preparation method and application as photocatalyst | |
| CN113289647A (en) | Biochar-doped BiOBrxCl1-xPhotocatalyst, preparation method and application | |
| CN109225311B (en) | Preparation method of composite oxide catalyst for catalyzing VOCs at low temperature | |
| CN107649145B (en) | A kind of catalyst for decomposing ozone and preparation method thereof | |
| CN114570348B (en) | Titanium dioxide-based nano composite photocatalyst for photocatalytic degradation by irradiation of visible light and application thereof | |
| CN109772442B (en) | Supported composite transition metal oxide, preparation method and application as catalyst | |
| CN110882699B (en) | Photocatalyst based on triple heterojunction structure and preparation method thereof | |
| CN116060015B (en) | Synthesis method of photo-thermal synergistic adsorption catalyst | |
| CN114602489B (en) | High-stability non-noble metal-based formaldehyde catalyst and preparation method thereof | |
| CN104815656A (en) | Nano CuO/TiO2 photocatalyst and preparation method of same | |
| CN116139848A (en) | A kind of preparation method and application of ZnO-TiO2 composite airgel | |
| CN113198461A (en) | Nano MnO2PTFE composite material and preparation method and application thereof | |
| CN116037188B (en) | Double-function supported high-efficiency non-noble metal catalytic material and preparation method and application thereof | |
| CN110605117A (en) | Ag-loaded nano TiO with atomic-level dispersion2Process for preparing catalyst | |
| CN116060080B (en) | A composite metal oxide catalyst and its preparation method and application | |
| CN116212630B (en) | Concentrated efficient deodorant and preparation method thereof | |
| CN114522741B (en) | Preparation method of amino-modified manganese oxide for enhancing formaldehyde removal efficiency and service life | |
| CN112427044B (en) | Nitrogen-doped mixed crystal titanium dioxide photocatalytic material, preparation method and application thereof | |
| CN103480352B (en) | TiO 2tiO in-ACF catalysis material 2crystal formation control method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |