CN113731497B - CdS QDs supported BPEI modified niobium pentoxide catalyst and preparation method and application thereof - Google Patents
CdS QDs supported BPEI modified niobium pentoxide catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN113731497B CN113731497B CN202111066279.XA CN202111066279A CN113731497B CN 113731497 B CN113731497 B CN 113731497B CN 202111066279 A CN202111066279 A CN 202111066279A CN 113731497 B CN113731497 B CN 113731497B
- Authority
- CN
- China
- Prior art keywords
- bpei
- catalyst
- cds qds
- modified
- supported
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000707 layer-by-layer assembly Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 239000003607 modifier Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000010955 niobium Substances 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000005576 amination reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims 20
- 238000010438 heat treatment Methods 0.000 claims 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims 1
- 229920002873 Polyethylenimine Polymers 0.000 claims 1
- FRLJSGOEGLARCA-UHFFFAOYSA-N cadmium sulfide Chemical class [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- 238000001338 self-assembly Methods 0.000 claims 1
- 230000003068 static effect Effects 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000011068 loading method Methods 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 241000282414 Homo sapiens Species 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- 206010006458 Bronchitis chronic Diseases 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 108010061951 Methemoglobin Proteins 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 208000007443 Neurasthenia Diseases 0.000 description 1
- 206010038731 Respiratory tract irritation Diseases 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 208000007451 chronic bronchitis Diseases 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000005265 lung cell Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B01J35/39—
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a CdS QDs loaded on a BPEI modified Nb 2 O 5 Catalyst, preparation method and application, firstly modifying Nb by modifier BPEI 2 O 5 Grafting amino groups on the carrier by an electrostatic self-assembly method to enable the carrier to have positive charges, and loading CdS QDs with negative charges on Nb modified by BPEI by the electrostatic self-assembly method 2 O 5 To obtain CdS QDs/BPEI-Nb 2 O 5 Then introducing visible light into a reaction system for catalytic oxidation of NO at the temperature of the catalyst chamber. CdS QDs/BPEI-Nb 2 O 5 With BPEI-Nb 2 O 5 And Nb (Nb) 2 O 5 In contrast, under visible light, cdS QDs/BPEI-Nb 2 O 5 Catalyst ratio BPEI-Nb 2 O 5 And Nb (Nb) 2 O 5 Performance of catalyst in removing NO by photocatalysis and NO 3 ‑ The selectivity of the catalyst is obviously improved. The room temperature photocatalytic oxidation technology is mild, efficient, economical and environment-friendly, and the method is simple and feasible, so that the method is beneficial to being applied to the removal of low-concentration NO in the atmosphere or indoor.
Description
Technical Field
The invention belongs to the field of environmental protection and air purification, and in particular relates to a CdS QDs loaded on a BPEI modified Nb 2 O 5 The catalyst and the preparation method and application thereof can obviously improve the NO removal efficiency under visible light.
Background
Since the 70 s of the last century, environmental pollution such as acid rain, greenhouse effect, ozone layer cavity, water pollution, etc., has been continuously worsened, which has seriously jeopardized the normal life and health of human beings. Wherein, in the urban atmospheric pollution of China, the automobile exhaust emission accounts for more than 70 percent. Since 1886 the first automobile is born, the highly developed automobiles in logistics technology and transportation technology bring convenience and rapidness to human beings, and become an indispensable transportation means for human beings, but everything is beneficial and disadvantageous, and we see that the automobile industry is continuously increasing in high-speed development, automobile yield and conservation amount, and according to incomplete statistics, the total amount of private automobiles in China in 2020 reaches 2.6 hundred million. Although the national stringent standards for automobile exhaust emissions have been met, certain toxic gases such as carbon monoxide, hydrocarbons, lead and sulfur oxides, in particular the nitrogen oxides NO, inevitably occur in automobile exhaust x . NO, in addition to being derived from automobile exhaust x But also from the combustion of stationary power fuels (e.g., coal, oil, etc.) from large chemical plants. NO (NO) x As one of the main pollutant sources causing the atmospheric pollution, it causes numerous negative effects on the ecological environment, such as acid rain, photochemical smog, depletion of ozone layer, greenhouse effect (indirect effect), etc. Long-term exposure of humans to nitrogen oxides can cause chronic sphagitis, chronic bronchitis, etc., as well as various degrees of neurasthenia syndrome and dental erosion. In addition, nitrogen oxides can also induce lung cell carcinogenesis. Human inhalation of nitric oxide can cause methemoglobin in addition to respiratory tract irritation.
Currently, NO x The removal of (95% is NO) mainly comprises the methods of pretreatment of fuel combustion, improvement of combustion mode, post-treatment of tail gas and the like. The pretreatment method of combustion mainly refers to denitrification treatment of fuel, so as to reduce NO in tail gas in the combustion process x But due to cost and laborThe process is limited, and the current denitrification process is not well developed and researched. The improvement of the combustion mode mainly adopts an air staged combustion technology, a fuel staged combustion technology, a smoke recycling and re-combustion technology and the like. The main concern of the automobile exhaust is the technology of purifying the inside of the engine, such as improving the structure, working mode and control device of the engine, so as to improve the combustion efficiency and reduce NO x For the purpose of the discharge amount. The technology of exhaust gas aftertreatment is still capable of reducing NO x The most effective method is the method with the two most widely studied and applied methods of catalytic oxidation and catalytic reduction.
Catalytic oxidation of NO and traditional NO x Is very similar. Mainly refers to NO which is directly oxidized to generate hydrophilic phase under the action of a catalyst at a lower concentration 3 - And NO 2 - Adsorbing on the surface of the solid phase catalyst, and finally transferring to liquid phase for removal through water washing. It mainly involves the following reactions:
in addition, NO oxidation is also a key step in nitrogen oxide storage reduction (NSR), industrial denitration Selective Catalytic Reduction (SCR), and Selective Catalytic Oxidation (SCO) in the removal of high-concentration automobile exhaust.
In addition, the low-concentration NO photocatalytic oxidation removal has good application prospects indoors and outdoors, the low-concentration NO can be directly oxidized by means of indoor lamplight or outdoor sunlight, nitrate and nitrite adsorbed on the surface of the catalyst are washed away by indoor manual wiping or outdoor rain washing, so that the photocatalyst shows good photocatalytic activity again, and the catalyst is recycled.
Thus, how to increase the activity of NO removal and the activity of NO at room temperature 3 - Is capable of reducing NO 2 Has important significance for purifying low-concentration NO in the atmosphere or indoor environment.
Disclosure of Invention
The method can improve the NO removal performance of the loaded CdS QDs catalyst by introducing visible light at room temperature. The method aims to overcome the defect of NO removal by photocatalysis at room temperature, improve the activity and nitrate radical selectivity of the catalyst at room temperature, and reduce NO 2 Provides a modified Nb in BPEI loaded with CdS QDs 2 O 5 Catalyst, preparation method and application thereof. By loading CdS QDs in BPEI modified Nb 2 O 5 The performance of the CdS QDs supported catalyst for catalyzing and removing NO is improved by utilizing the effect of visible light, the problems of instability and low activity of the conventional CdS QDs supported catalyst and a simple carrier in the photocatalytic oxidation process are solved, and the preparation method of the catalyst is simple and feasible and is favorable for popularization and application.
In order to achieve the above purpose, the invention adopts the following technical scheme:
nb modified by BPEI loaded with CdS QDs 2 O 5 Catalyst of BPEI-Nb 2 O 5 The CdS QDs are used as carriers, and the active component is used as a high-dispersion supported photocatalyst, wherein the content of the active component CdS QDs is 0.1-3 wt%.
The supported CdS QDs catalysts as described above are capable of achieving photocatalytic removal of low concentrations of NO at room temperature under visible light and remain stable during the test cycle.
The preparation method of the supported CdS QDs catalyst adopts BPEI as a modifier and realizes Nb through the action of electrostatic self-assembly 2 O 5 Grafting an amino group on the carrier; in the obtained BPEI-Nb by using an electrostatic self-assembly method 2 O 5 The active component CdS QDs are loaded on the carrier, which comprises the following steps:
(1) Dissolving ammonium niobium oxalate in deionized water, and dropwise adding H after the ammonium niobium oxalate is completely hydrolyzed 2 O 2 Stirring for 30 min, placing in autoclave, centrifuging at 150-180deg.C under hydrothermal condition 12-18 h, washing with deionized water for several times, and drying at 60-80deg.C for 8-12 h to obtain Nb 2 O 5 The precursor is put into a crucible and calcined at 400-600 ℃ for 4-6 h to obtain Nb 2 O 5 A carrier.
(2) BPEI and Nb 2 O 5 Dissolving in absolute ethanol, ultrasonic treating 2 h, refluxing the mixture in water bath for 4 h, centrifuging, washing with absolute ethanol and deionized water for several times, and drying at 80deg.C to obtain aminated Nb 2 O 5， I.e. BPEI-Nb 2 O 5 。
(3) To a certain amount of CdCl 2 And MPA in deionized water and the PH was adjusted to about 10 by dropwise addition of NaOH solution. The solution was placed in a three-necked flask, and air was purged and replaced with argon. Freshly prepared Na is then added 2 The S solution was added to the mixture solution at room temperature to give a bright yellow transparent solution. Subsequently, the reaction mixture was heated to 100℃and condensed at reflux. Finally, the bright yellow transparent solution was kept under stirring at 100 ℃ for about 0.5. 0.5 h, thereby promoting the growth of CdS QDs. After cooling, the precipitate was separated by centrifugation with the addition of ethanol and then redispersed in water for further use.
(4) The CdS QDs and the BPEI-Nb are added in certain amounts 2 O 5 Mixing in deionized water, refluxing in water bath for 4 h, centrifuging, washing with deionized water for several times, and drying at 80deg.C to obtain Nb with CdS QDs supported on BPEI modification 2 O 5 I.e. CdS QDs/BPEI-Nb 2 O 5 。
The concentration of the CdS QDs solution is 1 mg/mL; the concentration of the NaOH solution is 5 mol/L.
The obtained supported CdS QDs catalyst can be used for removing low-concentration NO in the atmosphere or indoor environment.
The invention has the remarkable advantages that:
(1) The invention uses Nb modified by BPEI 2 O 5 Obtain non-toxic green BPEI-Nb 2 O 5 As a carrier for the semiconductor, it was found that BPEI-modified Nb was found 2 O 5 The activity of NO removal is obviously improved, and the CdS QDs are supported on Nb when being supported on the semiconductor, and the activity of the CdS QDs is obviously improved 2 O 5 The light response is in the ultraviolet to visible region,the semiconductor can excite electron-hole pairs under the irradiation of visible light with a certain wavelength, and CdS QDs can also serve as hole sacrificial agents in a certain sense to capture holes, so that the recombination of electron-hole pairs is reduced, more superoxide radicals are generated, the absorption and activation of NO are facilitated, and the absorption and activation of NO+O are promoted 2 The reaction is carried out such that NO conversion and NO 3 - The selectivity of (c) is improved.
(2) The electrostatic self-assembly preparation method and the application operation are simple and feasible, and the electrostatic self-assembly preparation method and the application operation are suitable for popularization and application.
Drawings
FIG. 1 shows Nb obtained in example 1 2 O 5 、CdS QDs 、BPEI-Nb 2 O 5 Is a Zeta potential map of (2);
FIG. 2 is a graph showing the result of example 1 of 3wt% CdS QDs/BPEI-Nb 2 O 5 Is a BET diagram of (2);
FIG. 3 is a graph showing the result of example 1 of 3wt% CdS QDs/BPEI-Nb 2 O 5 An XRD pattern of (b);
FIG. 4 is a graph showing the result of example 1 of 3wt% CdS QDs/BPEI-Nb 2 O 5 Ultraviolet-diffuse reflectance spectrograms of (a).
Detailed Description
In order to make the above features and advantages of the present invention more comprehensible, embodiments accompanied with figures are described in detail below, but the present invention is not limited thereto.
Example 1
3 wt% CdS QDs/BPEI-Nb 2 O 5 The preparation of the catalyst comprises the following specific steps:
(1) Dissolving ammonium niobium oxalate in 65 mL deionized water, slowly dropwise adding 15 mLH after complete hydrolysis 2 O 2 Stirring for 30 min, centrifuging after hydrothermal treatment at 175 deg.C for 15 h in autoclave, washing with deionized water for several times, and drying at 80 deg.C for 12 h to obtain Nb 2 O 5 The precursor is put into a crucible to be calcined at 400 ℃ for 4 h to obtain Nb 2 O 5 A carrier.
(2) 0.7 g of BPEI and 0.7 g of Nb 2 O 5 Dissolving in 70 mL anhydrous ethanol, ultrasonic treating 2 h, and mixingReflux 4 h in water bath at 70deg.C, centrifuging, washing with absolute ethanol and deionized water for several times, and drying at 80deg.C to obtain aminated Nb 2 O 5 I.e. BPEI-Nb 2 O 5 。
(3) 1 mmole of CdCl 2 And 1.7 mmole of MPA were mixed in 20 mL deionized water and the pH was adjusted to about 10 by dropwise addition of NaOH solution. The solution was placed in a three-necked flask, in which air was evacuated and replaced with Ar gas. Freshly prepared 1 mmole Na 2 The S solution was added to the mixture solution at room temperature to give a bright yellow transparent solution. Subsequently, the reaction mixture was heated to 100℃and condensed at reflux. Finally, the bright yellow transparent solution was kept under stirring at 100 ℃ for about 0.5. 0.5 h, thereby promoting the growth of CdS QDs. After cooling, the precipitate was separated by centrifugation with the addition of ethanol and then redispersed in water for further use.
(4) 30 mL of 1 mg/mL CdS QDs solution and 1 g of BPEI-Nb 2 O 5 Mixing with 70 mL deionized water, refluxing at 70deg.C in water bath for 4 h, centrifuging, washing with deionized water for several times, and drying at 80deg.C to obtain Nb with CdS QDs supported on BPEI 2 O 5 I.e. 3wt% CdS QDs/BPEI-Nb 2 O 5 . By adding 5 mL, 10 mL of CdS QDs, 0.5 wt% of CdS QDs/BPEI-Nb 2 O 5 And 1 wt% CdS QDs/BPEI-Nb 2 O 5 。
Example 2
Evaluation of catalyst Performance
The performance evaluation of the catalyst is carried out in a self-designed miniature fixed bed normal pressure continuous reaction device, and the reaction device consists of a gas distribution system, a miniature quartz reaction tube, a humidifying system, a circulating condensing system, a temperature control display and a xenon lamp (420 nm < lambda < 760 nm). Wherein the micro quartz reactor is of a square sleeve double-layer structure, the inner tube filled with the catalyst has the size of 20 mm multiplied by 20 multiplied by mm multiplied by 0.5 mm, and the outer layer of the quartz reactor is used for controlling the reaction temperature through circulating water.
For the reaction of catalyzing and oxidizing NO, a catalyst with the particle size of 0.4-g of about 0.2-0.3 mm (60-80 meshes) is filled in a quartz reactor, and the reaction temperature is controlled to be 25 ℃ by using a circulating water bath, and the reaction gasThe concentration of NO in the stream was 10 ppm, O 2 21.0 vol% of the balance gas N 2 The gas flow rate of the reaction gas was controlled to be 100 mL/min (ghsv=30,000 h -1 ) Covering the reactor with aluminum foil in dark reaction, taking NO concentration for 30 min as balance value, introducing visible light under the same condition for 30 min, and using Thermo Scientific Model 42i type NO at the tail gas port x On-line recording of NO and NO by analyzer 2 Is a concentration change of (c). The gas-solid phase reaction device is shown in figure 2-1, and NO is converted and converted 2 Conversion and NO x The conversion calculation formula is as follows:
here, [ NO ]] in And [ NO ]] out NO concentration at the air inlet and the air outlet respectively; [ NO ] 2 - ]And [ NO ] 3 - ]Namely nitrite and nitrate concentrations.
The amounts of nitrate and nitrite accumulated during the catalytic oxidation of NO were determined by a model Thermo Fisher Dionex Aquion ion chromatography test. The specific method comprises the following steps: the catalyst sample after continuous reaction is fully immersed in deionized water of 35 mL, washed and filtered to obtain supernatant, and then 5 mL is filled into an ion chromatographic tube for sample injection analysis. Total NO removal (n NO ) And NO 2 Amount of formation (n) NO2 ) Calculated using the following formula:
here, ƒ is the gas flow rate in the standard state, Φ NO Is the concentration of NO in the air inlet phi NOi Is the concentration of NO at the air outlet phi NO2 Air outlet NO 2 Is a concentration of (3).
The catalytic NO removal performance of each catalyst was evaluated in this manner, and the results are shown in the following table:
TABLE 1 CdS QDs/BPEI-Nb content before and after visible light irradiation 2 O 5 Catalytic NO removal performance at rh=50%
As shown by the results in the above table, for each catalyst, it is compared with Nb 2 O 5 Nb modified by BPEI under the action of visible light 2 O 5 The NO removal is obviously improved, the conversion rate of 72.01 percent can be achieved, and NO is generated 2 The conversion rate is also obviously reduced, but most of NO is generated 2 - ，NO 3 - Is lower. When NO removal is further enhanced by the loading of CdS QDs, 100% conversion can be achieved, and NO 2 Is in a decreasing trend and NO 3 - Further improved conversion of (c) is obtained. It can be seen that under the action of visible light, the performance of the catalyst for removing NO and NO by catalysis can be improved 3 - Is selected from the group consisting of (1).
As can be seen from fig. 1, nb 2 O 5 The Zeta potential of the carrier is negatively charged, while the Zeta potential of the CdS QDs also appears negative. For Nb by BPEI 2 O 5 Modification of the amination of the support to allow Nb to be 2 O 5 The carrier surface has positive charges, and CdS QDs have negative charges, so that the CdS QDs are loaded on Nb by adopting an electrostatic self-assembly mode by utilizing the difference of the charging property of the two materials 2 O 5 A carrier; as can be seen from FIG. 2, cdS QDs/BPEI-Nb 2 O 5 The catalyst has larger specific surface area, larger pore volume and smaller pore diameter, and has very large promotion effect on the adsorption and activation of NO; as can be seen from FIG. 3, only Nb appears in XRD patterns of the catalyst due to low CdS QDs content 2 O 5 This also illustrates that the CdS QDs in the catalyst are uniformly dispersed; as can be seen from FIG. 4, cdS QDs/BPEI-Nb 2 O 5 Compared with Nb 2 O 5 The carrier has obvious red shift, is favorable for light absorption and plays a better photo-promotion role.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (8)
1. CdS QDs is loaded on BPEI modified Nb 2 O 5 The preparation method of the catalyst is characterized in that: the catalyst is Nb modified by branched polyethyleneimine 2 O 5 The catalyst is a carrier, and the cadmium sulfide quantum dots are high-dispersion supported catalysts with active components; wherein the content of CdS QDs in the catalyst is 0.5-3 wt%;
the preparation method is that BPEI is used as modifier to realize Nb by an electrostatic self-assembly method 2 O 5 Amination, making it positively charged; and the static self-assembly method is utilized again to obtain the BPEI-Nb 2 O 5 The active component CdS QDs is loaded on the carrier.
2. The CdS QDs supported on BPEI modified Nb of claim 1 2 O 5 The preparation method of the catalyst is characterized in that: the method comprises the following steps:
(1) Preparation of Nb by hydrothermal method 2 O 5 A carrier;
(2) Amination of the carrier prepared in the step (1) by using BPEI as a modifier and using an electrostatic self-assembly method to obtain BPEI-Nb 2 O 5 ；
(3) BPEI-Nb prepared in step (2) by using electrostatic self-assembly method 2 O 5 Active component CdS QDs are loaded to obtain Nb modified by BPEI loaded with CdS QDs 2 O 5 A catalyst.
3. The CdS QDs supported on BPEI modified Nb of claim 2 2 O 5 The preparation method of the catalyst is characterized in that: the step (1) comprises the following steps: dissolving ammonium niobium oxalate in deionized water, and dropwise adding H after the ammonium niobium oxalate is completely hydrolyzed 2 O 2 Stirring for 30 min, placing in an autoclave, centrifuging at 150-180deg.C under water heating of 12-18 h, washing with deionized water, and drying at 60-80deg.C for 8-12 h to obtain Nb 2 O 5 Precursor, and placing the precursor in a crucible at 400-600deg.CCalcining 4-6 h to obtain Nb 2 O 5 A carrier.
4. The CdS QDs supported on BPEI modified Nb of claim 2 2 O 5 The preparation method of the catalyst is characterized in that: the step (2) comprises the following steps: BPEI and Nb of step (1) 2 O 5 Dissolving in absolute ethanol, ultrasonic treating 2 h, refluxing in water bath for 4 h, centrifuging, washing with absolute ethanol and deionized water, and drying at 80deg.C to obtain aminated Nb 2 O 5 I.e. BPEI-Nb 2 O 5 。
5. The CdS QDs supported on BPEI modified Nb of claim 2 2 O 5 The preparation method of the catalyst is characterized in that: the step (3) is specifically as follows: cdCl is firstly put into 2 And mercaptopropionic acid were mixed in deionized water and the pH was adjusted to 10 by dropwise addition of NaOH solution, the solution was placed in a three-necked flask, air was purged and replaced with argon, and freshly prepared Na was then taken in 2 Adding S solution into the mixture solution at room temperature to obtain bright yellow transparent solution, heating the reaction mixture to 100deg.C, condensing and refluxing, stirring at 100deg.C for 0.5. 0.5 h to promote CdS QDs growth, cooling, centrifuging to obtain precipitate by adding ethanol to obtain CdS QDs, and adding the precipitate and BPEI-Nb obtained in step (2) 2 O 5 Mixing in deionized water, refluxing in water bath for 4 h, centrifuging, washing with deionized water for several times, and drying at 80deg.C to obtain Nb with CdS QDs supported on BPEI modification 2 O 5 That is, cdS QDs are supported on BPEI modified Nb 2 O 5 A catalyst.
6. The CdS QDs supported on BPEI modified Nb of claim 5 2 O 5 The preparation method of the catalyst is characterized in that: the CdS QDs and the BPEI-Nb 2 O 5 The concentration of CdS QDs mixed in deionized water is 1 mg/mL; the concentration of the NaOH solution is 5 mol/L.
7. A process according to claim 1, wherein CdS QDs are supported on BPEI-modified Nb 2 O 5 The application of the catalyst is characterized in that: the CdS QDs are loaded on the Nb modified by the BPEI 2 O 5 The catalyst is applied to the removal of low-concentration NO in the atmosphere or indoor environment.
8. The CdS QDs supported on BPEI modified Nb of claim 7 2 O 5 The application of the catalyst is characterized in that: nb modified in BPEI (binary electric element) on CdS QDs (cadmium sulfide) load 2 O 5 The catalyst introduces visible light into a reaction system for catalyzing and oxidizing NO at room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111066279.XA CN113731497B (en) | 2021-09-13 | 2021-09-13 | CdS QDs supported BPEI modified niobium pentoxide catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111066279.XA CN113731497B (en) | 2021-09-13 | 2021-09-13 | CdS QDs supported BPEI modified niobium pentoxide catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113731497A CN113731497A (en) | 2021-12-03 |
| CN113731497B true CN113731497B (en) | 2023-06-16 |
Family
ID=78738230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111066279.XA Active CN113731497B (en) | 2021-09-13 | 2021-09-13 | CdS QDs supported BPEI modified niobium pentoxide catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113731497B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618527B (en) * | 2022-03-23 | 2023-05-23 | 河南大学 | Au nanoparticle and CdS quantum dot modified niobate composite nanomaterial and application thereof |
| CN115282962A (en) * | 2022-08-11 | 2022-11-04 | 福州大学 | Silver nanoparticle modified niobium pentoxide photocatalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350346A (en) * | 2011-08-09 | 2012-02-15 | 福州大学 | Preparation method of visible light catalyst with surface plasmon effect and application thereof |
| CN104289227A (en) * | 2014-09-25 | 2015-01-21 | 哈尔滨工业大学深圳研究生院 | Mn, Co, Ce and Ti four-component NH3-SCR supported catalyst for low-temperature flue gas denitrification |
| CN108607593A (en) * | 2016-01-26 | 2018-10-02 | 苏州大学 | Niobium pentoxide nano stick/nitrogen-doped graphene composite photo-catalyst of cadmium sulfide nano-particles modification and application |
| CN113210003A (en) * | 2021-05-25 | 2021-08-06 | 南京奇安威尔环境科技有限公司 | Preparation method of composite visible-light-driven photocatalyst graphene quantum dot/graphite-phase nitrogen carbide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017155120A1 (en) * | 2016-03-11 | 2017-09-14 | 東洋合成工業株式会社 | Supported metal catalyst |
-
2021
- 2021-09-13 CN CN202111066279.XA patent/CN113731497B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350346A (en) * | 2011-08-09 | 2012-02-15 | 福州大学 | Preparation method of visible light catalyst with surface plasmon effect and application thereof |
| CN104289227A (en) * | 2014-09-25 | 2015-01-21 | 哈尔滨工业大学深圳研究生院 | Mn, Co, Ce and Ti four-component NH3-SCR supported catalyst for low-temperature flue gas denitrification |
| CN108607593A (en) * | 2016-01-26 | 2018-10-02 | 苏州大学 | Niobium pentoxide nano stick/nitrogen-doped graphene composite photo-catalyst of cadmium sulfide nano-particles modification and application |
| CN113210003A (en) * | 2021-05-25 | 2021-08-06 | 南京奇安威尔环境科技有限公司 | Preparation method of composite visible-light-driven photocatalyst graphene quantum dot/graphite-phase nitrogen carbide |
Non-Patent Citations (1)
| Title |
|---|
| Nb2O5 /CdS 纳米粒子的制备及其光催化性能研究;黄正喜等;《中南民族大学学报( 自然科学版)》;第33卷(第4期);第26-30页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113731497A (en) | 2021-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113731497B (en) | CdS QDs supported BPEI modified niobium pentoxide catalyst and preparation method and application thereof | |
| CN102247877B (en) | Preparation method of visible light catalyst | |
| CN107185493B (en) | Preparation method of graphene modified composite mesoporous carbon microsphere air purifying agent | |
| CN107952449B (en) | Low-temperature synergistic denitration, dioxin and mercury removal honeycomb catalyst and preparation method thereof | |
| CN106064101A (en) | A kind of iron-based MOFs catalysis material and preparation and application thereof | |
| CN108722464B (en) | Pd three-way low-temperature catalyst with nitrogen-doped titanium dioxide as carrier and preparation method and application thereof | |
| CN113786842B (en) | Catalyst for synthesizing ammonia from NO oxide, preparation method and application thereof | |
| CN101804344A (en) | Manganese/carbon nanotube denitrification catalytic reduction catalyst and preparation method thereof | |
| CN108786859A (en) | A kind of preparation method of carbon doping iodine oxygen bismuth acid iodide oxygen bismuth heterojunction structure | |
| CN113117704A (en) | Preparation method and application of modified nano titanium dioxide photocatalyst | |
| CN111686716B (en) | WOxLow-temperature SCR (selective catalytic reduction) flue gas denitration catalyst with modified carbon nano tube loaded with metal oxide, and preparation method and application thereof | |
| Lu et al. | Oxygen vacancy engineering of photocatalytic nanomaterials for enrichment, activation, and efficient removal of nitrogen oxides with high selectivity: a review | |
| CN1883775A (en) | Photo-catalytic oxidation and wet method absorption combined wet method flue-gas denitration process | |
| CN103721710B (en) | A kind of supported Pt catalysts and its preparation method and application | |
| CN112691542B (en) | Metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs (volatile organic compounds), and preparation method and application thereof | |
| CN1269568C (en) | Composite nano-photo-catalyst used for purifying air | |
| CN113731445B (en) | Photocatalyst taking barium stannate as carrier to load cadmium sulfide quantum dots, and preparation method and application thereof | |
| CN103877855A (en) | Method for removing null-valence mercury in waste gas through photocatalytic oxidation and adsorption | |
| CN107020138B (en) | A kind of Supported Pd-Catalyst and its preparation method and application | |
| Mengjie et al. | Application of and research on TiO2 photocatalysis technology | |
| CN112221488A (en) | Novel core-shell structure catalyst for synergistic denitration and demercuration and preparation method thereof | |
| CN108837694B (en) | Method for removing zero-valent mercury and fixing ionic mercury from flue gas | |
| CN108014819B (en) | Preparation method and application of titanium dioxide photocatalyst | |
| CN107673441B (en) | Method for degrading rhodamine B under irradiation of ultraviolet lamp light source | |
| CN115301253A (en) | Pd/ferroferric oxide catalyst for photo-assisted production of ammonia from NO, and preparation method and application thereof |
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 |