CN114733573A - Bismuth titanate @ NH2Preparation and application of-MIL-125 photocatalyst - Google Patents
Bismuth titanate @ NH2Preparation and application of-MIL-125 photocatalyst Download PDFInfo
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- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 38
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 24
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000008030 elimination Effects 0.000 claims abstract description 12
- 238000003379 elimination reaction Methods 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 9
- 238000011160 research Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
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- 239000005977 Ethylene Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 abstract description 31
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 7
- 238000005530 etching Methods 0.000 abstract description 6
- 239000003446 ligand Substances 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 238000009825 accumulation Methods 0.000 abstract 1
- 238000007210 heterogeneous catalysis Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 62
- 239000013086 titanium-based metal-organic framework Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
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- 239000007789 gas Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
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- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical class OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
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- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100001143 noxa Toxicity 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
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- 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
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- 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
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract
On the basis of the accumulation of the previous research work, the invention designs a MOFs photocatalyst with a titanium-based metal cluster as a central node and an amino-containing photosensitive matrix as a ligand, and prepares novel high-efficiency bismuth titanate @ NH by utilizing an in-situ etching regeneration strategy2The MIL-125 composite catalytic catalyst develops a new stable, green and efficient photocatalytic NO elimination way, deeply studies the basic relationship between the structure and the performance, and constructs a diversified MOFs photocatalyst molecular library. Meanwhile, based on reasonable molecular structure design, the basic rules of in-situ etching of bismuth nitrate pentahydrate with different contents and the structure and catalytic performance of MOFs materials are deeply explored, and the application prospect of the MOFs materials in the field of heterogeneous catalysis such as visible light photocatalytic NO elimination is developed. By adjusting the quality of the bismuth nitrate pentahydrate, the bismuth nitrate pentahydrate is foundMass and NH2When the mass ratio of-MIL-125 is 4:10, the in-situ etching effect is best, and the NO elimination effect is best.
Description
Technical Field
The invention relates to the technical field of photocatalytic NO elimination, and particularly relates to bismuth titanate @ NH2-synthesis and application of MIL-125 photocatalyst.
Background
In recent years, environmental pollution has been increasing, in which air pollution such as Nitrogen Oxides (NO) is occurringx) Sulfur dioxide (SO)2) Contamination is of great concern. Nitrogen Oxides (NO)x) The emissions of (d) are mainly toxic gases generated by burning nitrogen-containing sources during agricultural activities, deforestation, industrialization, energy production, transportation and other human activities, causing serious environmental disasters including acid rain, smog, particulate matter release and greenhouse effect. In addition, human or animal and NOxCan cause a variety of toxicological responses, depending on the duration of exposure and NOxAnd (4) concentration. Thus, study of NOxRemoval techniques are a highly important task, as has been established in the last decadesThe current situation is reflected by many catalytic and non-catalytic processes.
In general, catalytic NO is compared to non-catalytic processesxThe removal process has higher efficiency and lower reaction temperature. However, conventional catalytic NOxThe temperature required for removal is still high. To solve this problem, photocatalytic NO is proposedxIncluding photocatalytic oxidation, photocatalytic decomposition and photo-selective catalytic reduction (photo-SCR). In particular, NOxPhotocatalytic oxidation of to produce NO2And finally nitrate to be washed off from the photocatalyst surface, and the reduction method of photo-SCR and photocatalytic decomposition can convert NO into N2And other harmless products. Photocatalytic NOxThe removal has many advantages, e.g., excellent N2Selectivity and appreciable NO at ambient temperature and pressurexConversion rate, cost effectiveness, sunlight-based environmental energy collection, no need of additional heat (energy saving), and production of nitrate as a raw material of fertilizer. Due to NOxFormed mainly in the combustion of automobile exhaust and fossil fuels, and is therefore preferred for the abatement of urban and atmospheric NOxA contaminated photocatalytic technique. It can be applied to actual commercial objects such as cement composite materials, concrete for highways, sidewalks, disinfection filters, and the like.
MOFs are a new type of porous structural materials which are developed rapidly in recent years, and are also called porous coordination polymers, and a type of porous crystalline material with a periodic multidimensional network structure is formed by self-assembly of metal ions or central metal clusters and organic ligands through coordination, and the coordination structure of the porous crystalline material exists in different types of 1D, 2D or 3D. Since the number of metal and ligand combinations is not limited, MOFs having a variety of physical properties, tunable porous properties and a number of chemical functional groups with high porosity and large specific surface area, up to 1000m, can be synthesized2·g-1Making it an excellent candidate for gas adsorption and separation, and in addition, MOFs contain metal nano-nodes similar to semiconductors, and thus can mimic certain properties found in quantum dots, including their photocatalytic capabilities. These properties of MOFs are very well matched to zeolites as well as semiconducting metal oxides. Thus, MOFs can in principle be designed as photocatalysts for gas treatment driven by visible light. The instability of MOFs in humid environments, in contrast to inorganic semiconductors, is one of the biggest drawbacks that limit their applications. The instability of MOFs is influenced by many factors, including the nature of the metal and organic ligands, coordination sites, operating environment, etc. Certain MOFs that have a strong structure and strong bonding and comply with the hard/soft/acid/base principle are considered to have a more stable framework under humid conditions.
Compared with conventional semiconductors, MOFs have the following unique advantages in photocatalysis: (1) the perfect crystal ordered structure of the MOFs is beneficial to reducing the recombination of photo-generated electrons and holes. (2) High porosity of MOFs: the porous structure provides additional exposed active sites and catalytic substrate (product) transport channels for the MOFs, thereby facilitating rapid transfer and utilization of photogenerated charges. (3) Structural adjustability of MOFs: long wavelength absorbing groups can be used as organic bridging ligands (e.g., -NH)2) The MOFs are introduced to enhance the light response range of the MOFs and increase the number of photo-generated electron-hole pairs. (4) Diverse compound structures: MOFs can easily combine with other compounds (e.g., photosensitizers and other co-catalysts) to form heterojunctions or schottky junctions and facilitate the generation and separation of photogenerated electrons and holes. Therefore, MOFs-based photocatalysts have gradually been considered as the most promising materials for introducing photocatalytic technology into practical applications.
Of the many types of MOFs, there is tetravalent Ti4+Cationic Ti-based MOFs (Ti-MOFs) appear to be a very attractive class of MOFs, not only showing strong metal-ligand bonding and rigid backbones, but also having good redox activity. Ti-MOFs play an important role in the MOFs family, providing perfect structural topology, excellent photocatalytic activity, low toxicity, abundant content and relatively low cost. By controlling the synthesis parameters (e.g., titanium precursors and organic ligands), the diversity of Ti-MOFs is greatly expanded. The dense rigid skeleton structure may be formed by TiO2Clusters and organic linkers (including phenolates, carboxylates, salicylatesAcid salts and catecholates) are tightly linked. Previous studies have shown that Ti-MOFs with nanoscale Ti-oxo clusters can be used as photocatalysts for renewable energy conversion and environmental pollution remediation. The application mainly focuses on the following aspects: hydrogen production, NO elimination, organic modification and pollutant degradation. Like most single-component photocatalysts, Ti-MOFs suffer from low photoresponse and fast electron-hole recombination rates. In addition, the low conductivity of MOFs also hinders their application in the field of photocatalysis.
Thus, a bismuth titanate @ NH is synthesized2MIL-125 photocatalyst material and its use in photocatalytic NO elimination studies are the direction of research by those skilled in the art.
Disclosure of Invention
The invention aims to synthesize bismuth titanate @ NH2-MIL-125 photocatalyst material of bismuth titanate and NH2-full play of a synergistic mechanism in the MIL-125 photocatalytic process to achieve excellent photocatalytic NO elimination effect.
The technical scheme adopted by the invention is as follows:
bismuth titanate @ NH2A method for preparing an MIL-125 photocatalyst, comprising the steps of:
(1) reacting NH2-MIL-125 in 50mLHNO3Adding bismuth nitrate pentahydrate into the (1mmol/L) aqueous solution, carrying out ultrasonic treatment for 15min to dissolve the bismuth nitrate pentahydrate, and then stirring the mixed solution at room temperature for reaction for 7 h;
(2) centrifuging and washing the solid obtained in the step (1) with deionized water and absolute ethyl alcohol for three times;
(3) vacuum drying the solid obtained in the step (2) at 80 ℃ for 12h to obtain bismuth titanate @ NH2-MIL-125。
Wherein, NH in the step (1)2The mass of-MIL-125 is 300mg, and the mass of bismuth nitrate pentahydrate is 120 mg.
Further, NH2-MIL-125 was prepared as follows:
(1) dissolving 2-amino terephthalic acid in a mixed solution of anhydrous methanol and anhydrous N, N-dimethylformamide, adding titanium isopropoxide, stirring for 10min, pouring the mixture into a poly-tetra-ethylene reaction kettle, placing the mixture in an oven, keeping the temperature of the mixture at 110 ℃ for 72h, standing and cooling the mixture to room temperature after the reaction is finished;
(2) immersing the solid obtained by centrifugation in the step (1) into DMF and methanol in sequence for twice and carrying out centrifugal washing;
(3) vacuum drying the solid obtained in the step (2) at 100 ℃ for 12h to obtain NH2-MIL-125。
Wherein the amount of the substance of 2-aminoterephthalic acid in the step (1) is 15.8mmol, and the amount of the substance of titanium isopropoxide is 9.7 mmol.
The invention also provides bismuth titanate @ NH2-use of MIL-125 material, said bismuth titanate @ NH2The MIL-125 material is suitable for photocatalytic NO elimination research and shows better effect.
Compared with the prior art, the invention has the following advantages:
1. compared with the original MOFs photocatalyst, the MOFs material after in-situ etching regeneration realizes the adjustment of the central metal node of the titanium-based MOFs, and meanwhile, the particles of the nano bismuth titanate can be highly dispersed on the outer surface of the MOFs, so that a large number of catalytic active sites are provided, the recombination of photo-generated electron-hole pairs is effectively inhibited, and the separation efficiency of photo-generated carriers is further improved.
2. The titanium-based MOFs metal cluster is regenerated and modified through in-situ etching, particles of nano bismuth titanate are highly dispersed on the outer surface of the MOFs, the expression formation and action rules among MOFs metal nodes, bismuth titanate and the MOFs are revealed from the angles of active sites, electron transfer paths and the like by combining a photochemical energy band transition theory and an energy band matching principle, and a new thought and a new method are provided for realizing the opening of clean energy sources in a diversified manner.
Drawings
FIG. 1 shows NH prepared in example 12XRD pattern of MIL-125.
FIG. 2 shows NH prepared in example 12-photocatalytic NO removal rate profile for MIL-125.
FIG. 3 shows bismuth titanate @ NH prepared in examples 2 to 52XRD pattern of MIL-125.
FIG. 4 shows examples 2 to 5Prepared bismuth titanate @ NH2-photocatalytic NO removal rate profile for MIL-125.
Detailed Description
The invention will be further explained with reference to the drawings and the embodiments.
Example 1:
NH2-a method for the preparation of MIL-125 comprising the steps of:
(1) 2-Aminoterephthalic acid (2.86g, 15.8mmol) was added to a mixed solution of 10mL of anhydrous methanol and 40mL of anhydrous N, N-dimethylformamide and stirred at room temperature until the 2-aminoterephthalic acid was completely dissolved. Next, titanium isopropoxide (2.86mL, 9.7mmol) was added to the above mixed solution, which was then transferred to a 100mL polytetrafluoroethylene-lined autoclave and heated at 110 ℃ for 72 h. Standing and cooling to room temperature;
(2) immersing the solid obtained by centrifugation in the step (1) into DMF and absolute methanol in sequence for twice and carrying out centrifugal washing;
(3) vacuum drying the solid obtained in the step (2) at the temperature of 100 ℃ for 12h to obtain NH2-MIL-125。
As shown in fig. 1. From the XRD pattern of FIG. 1, NH which was done with predecessor can be seen2The XRD pattern of-MIL-125 is consistent, indicating our NH2-MIL-125 was synthesized successfully.
To prepare NH2-MIL-125 material is used in photocatalytic NO elimination as follows:
the synthesized NH2The MIL-125 material (0.2g) was placed in two 12cm diameter glass dishes (100 mg per dish) and then ultrasonically dispersed by adding 10mL of ethanol. The dish was then dried at 60 ℃ and shaken during drying to disperse the sample evenly inside the dish until all the solvent had evaporated. After cooling to room temperature, the two dishes were used for further photocatalytic NO removal experiments. By NO-NO2-NOxThe analyser (Thermo Scientific, 42iTL) measures photocatalytic NO oxidation. The reaction was carried out in a continuous flow reactor, above which two conventional LED lamps (12W) were placed vertically. During each test, NO (initial concentration 100ppm) was first introduced and then the air generator was turned onThe NO concentration was diluted to 530 ppb. After the gas reaches the adsorption-desorption balance, turning on a lamp to start the illumination reaction.
FIG. 2 shows NH prepared2Graph of photocatalytic NO elimination results for MIL-125 material. FIG. 2 shows the NH prepared2The photocatalytic NO removal rate of the MIL-125 material was 19.87%.
Example 2:
bismuth titanate @ NH2-a method for the preparation of MIL-125(1:10) material comprising the steps of:
(1) taking 300mg of NH2-MIL-125 was poured into a clean beaker and 50mLHNO was added3Ultrasonic dissolving (1mmol/L) of the aqueous solution, adding 30mg of bismuth nitrate pentahydrate, ultrasonic dissolving for 15min, and stirring the mixed solution at room temperature for reaction for 7 h;
(2) centrifuging and washing the solid obtained in the step (1) with deionized water and absolute ethyl alcohol for three times;
(3) vacuum drying the solid obtained in the step (2) at the temperature of 80 ℃ for 12h to obtain bismuth titanate @ NH2-MIL-125(1:10)。
Example 3:
bismuth titanate @ NH2-a method for preparing MIL-125(4:10) material comprising the steps of:
(1) taking 300mg of NH2-MIL-125 was poured into a clean beaker and 50mLHNO was added3Ultrasonic dissolving (1mmol/L) of the aqueous solution, adding 120mg of bismuth nitrate pentahydrate, ultrasonic dissolving for 15min, and stirring the mixed solution at room temperature for reaction for 7 h;
(2) centrifuging and washing the solid obtained in the step (1) with deionized water and absolute ethyl alcohol for three times;
(3) vacuum drying the solid obtained in the step (2) at the temperature of 80 ℃ for 12h to obtain bismuth titanate @ NH2-MIL-125(4:10)。
Example 4:
bismuth titanate @ NH2-a method for the preparation of MIL-125(8:10) material comprising the steps of:
(1) taking 300mg of NH2-MIL-125 was poured into a clean beaker and 50mLHNO was added3(1mmol/L) of aqueous solution, ultrasonic dissolution,then adding 240mg of bismuth nitrate pentahydrate, carrying out ultrasonic treatment for 15min to dissolve the bismuth nitrate pentahydrate, and then stirring the mixed solution at room temperature for reaction for 7 h;
(2) centrifuging and washing the solid obtained in the step (1) with deionized water and absolute ethyl alcohol for three times;
(3) vacuum drying the solid obtained in the step (2) at 80 ℃ for 12h to obtain bismuth titanate @ NH2-MIL-125(8:10)。
Example 5:
bismuth titanate @ NH2-a method for preparing MIL-125(12:10) material comprising the steps of:
(1) taking 300mg of NH2-MIL-125 was poured into a clean beaker and 50mLHNO was added3Ultrasonic dissolving (1mmol/L) of the aqueous solution, adding 240mg of bismuth nitrate pentahydrate, ultrasonic dissolving for 15min, and stirring the mixed solution at room temperature for reaction for 7 h;
(2) centrifuging and washing the solid obtained in the step (1) with deionized water and absolute ethyl alcohol for three times;
(3) vacuum drying the solid obtained in the step (2) at the temperature of 80 ℃ for 12h to obtain bismuth titanate @ NH2-MIL-125(12:10)。
FIG. 3 shows bismuth titanate @ NH in production examples 2 to 52XRD pattern of MIL-125 material, from which it can be seen that in-situ etched regenerated bismuth titanate @ NH2XRD pattern of-MIL-125 (1:10), (4:10), with pure NH2MIL-125, and bismuth titanate @ NH2XRD of MIL-125(8:10), (12:10) showed new peaks, indicating bismuth nitrate pentahydrate: NH (NH)2New species appeared during in-situ etching with a mass ratio of-MIL-125 of 8:10 and 12: 10.
Example 6:
the bismuth titanate @ NH prepared in the above examples 2 to 52The MIL-125 materials were used in photocatalytic NO elimination, respectively, as follows:
the synthesized bismuth titanate @ NH2The MIL-125 material (0.2g) was placed in two 12cm diameter glass dishes (100 mg per dish) and then ultrasonically dispersed by adding 10mL of ethanol. Then, the glass dish is dried at 60 ℃, the glass dish is shaken during the drying, so that the sample is uniformly dispersed in the glass dish,until all the solvent has evaporated. After cooling to room temperature, the two dishes were used for further photocatalytic NO removal experiments. By NO-NO2-NOxThe analyser (Thermo Scientific, 42iTL) measures photocatalytic NO oxidation. The reaction was carried out in a continuous flow reactor, above which two conventional LED lamps (12W) were placed vertically. During each test, NO (initial concentration of 100ppm) was first fed and then the air generator was turned on to dilute the NO concentration to 530 ppb. After the gas reaches the adsorption-desorption balance, the lamp is turned on to start the illumination reaction.
Bismuth titanate @ NH prepared in examples 2 to 52The NO removal rate of the-MIL-125 material is shown in Table 1.
Referring to fig. 2, the NO removal rate of example 1 was 19.87%, while it can be seen from table 1 and fig. 4 that the NO removal rate of the catalyst of example 3 reached 57.76%, which is 2.9 times that of example 1. The superior performance may be attributed to enhanced visible light absorption and the formation of novel electron transfer pathways. However, it is seen from example 4 that as the mass of bismuth nitrate pentahydrate increases, the photocatalytic activity decreases, which may cause bismuth nitrate pentahydrate to be excessively large, blocking active centers, thereby decreasing the photocatalytic efficiency.
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that the technical solutions of the present invention can be modified or substituted with equivalent solutions without departing from the spirit and scope of the technical solutions, and all should be covered in the claims of the present invention.
Claims (5)
1. Bismuth titanate @ NH2A process for preparing the-MIL-125 photocatalyst, which comprisesThe following steps:
(1) reacting NH2-MIL-125 dissolved in HNO3Adding bismuth nitrate pentahydrate into the (1mmol/L) aqueous solution, carrying out ultrasonic treatment for 15min to dissolve the bismuth nitrate pentahydrate, and then stirring the mixed solution at room temperature for reaction for 7 h;
(2) centrifuging and washing the solid obtained in the step (1) with deionized water and absolute ethyl alcohol for three times;
(3) vacuum drying the solid obtained in the step (2) at the temperature of 80 ℃ for 12h to obtain bismuth titanate @ NH2-MIL-125。
2. The bismuth titanate @ NH of claim 12-MIL-125 photocatalyst, characterized in that, the NH of step (1)2The mass of-MIL-125 is 300mg, and the mass of bismuth nitrate pentahydrate is 120 mg.
3. The bismuth titanate @ NH of claim 12-MIL-125 photocatalyst, characterized in that, the NH is added2-MIL-125 was prepared as follows:
(1) dissolving 2-amino terephthalic acid in a mixed solution of anhydrous methanol and anhydrous N, N-dimethylformamide, adding titanium isopropoxide, stirring for 10min, pouring the mixture into a poly-tetra-ethylene reaction kettle, placing the mixture in an oven, keeping the temperature of the mixture at 110 ℃ for 72h, standing and cooling the mixture to room temperature after the reaction is finished;
(2) immersing the solid obtained by centrifugation in the step (1) into DMF and methanol in sequence for twice and carrying out centrifugal washing;
(3) vacuum drying the solid obtained in the step (2) at the temperature of 100 ℃ for 12h to obtain NH2-MIL-125。
4. The bismuth titanate @ NH of claim 32A method for preparing the MIL-125 photocatalyst, wherein the amount of the substance of 2-aminoterephthalic acid in the step (1) is 15.8mmol, and the amount of the substance of titanium isopropoxide is 9.7 mmol.
5. Bismuth titanate @ NH2-use of MIL-125 material, characterized in that said bismuth titanate @ NH2-MIL-125 material is prepared by the method of claims 1-4; the bismuth titanate @ NH2The MIL-125 material is used for photocatalytic NO elimination research and shows better effect.
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| CN115219572A (en) * | 2022-07-13 | 2022-10-21 | 重庆工商大学 | Method for detecting nitrate ions by MOFs electrode |
| CN115870010A (en) * | 2022-10-09 | 2023-03-31 | 苏州大学 | Bismuth titanate nanosheet/UiO-66-NH containing bismuth vacancies 2 Heterojunction and preparation method and application thereof |
| CN116273192A (en) * | 2023-03-30 | 2023-06-23 | 重庆工商大学 | Preparation method of photocatalyst |
| WO2024077411A1 (en) * | 2022-10-09 | 2024-04-18 | 苏州大学 | Bismuth titanate nanosheet/uio-66-nh2 heterojunction containing bismuth vacancies, preparation method therefor and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115219572A (en) * | 2022-07-13 | 2022-10-21 | 重庆工商大学 | Method for detecting nitrate ions by MOFs electrode |
| CN115219572B (en) * | 2022-07-13 | 2023-05-19 | 重庆工商大学 | Method for detecting nitrate ions by MOFs electrode |
| CN115870010A (en) * | 2022-10-09 | 2023-03-31 | 苏州大学 | Bismuth titanate nanosheet/UiO-66-NH containing bismuth vacancies 2 Heterojunction and preparation method and application thereof |
| WO2024077411A1 (en) * | 2022-10-09 | 2024-04-18 | 苏州大学 | Bismuth titanate nanosheet/uio-66-nh2 heterojunction containing bismuth vacancies, preparation method therefor and use thereof |
| CN116273192A (en) * | 2023-03-30 | 2023-06-23 | 重庆工商大学 | Preparation method of photocatalyst |
| CN116273192B (en) * | 2023-03-30 | 2024-04-19 | 重庆工商大学 | Preparation method of photocatalyst |
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