CN114985011A - TiO 2 2 Mxene/MOFs photocatalytic material and preparation method thereof - Google Patents
TiO 2 2 Mxene/MOFs photocatalytic material and preparation method thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 83
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 63
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000007146 photocatalysis Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000013110 organic ligand Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000005530 etching Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 150000007530 organic bases Chemical class 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical group [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 claims description 3
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract description 25
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000010842 industrial wastewater Substances 0.000 abstract 1
- 239000008235 industrial water Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 25
- 230000000694 effects Effects 0.000 description 14
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- 229910052724 xenon Inorganic materials 0.000 description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 10
- 239000010936 titanium Substances 0.000 description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 6
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000004298 light response Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 239000000138 intercalating agent Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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Abstract
The invention provides a TiO compound 2 The material is sheet TiO, MXene/MOFs photocatalysis material 2 /MXene and MOFs crystal assembled electrostatically to form flaky TiO 2 The mass ratio of MXene to MOFs crystal is 1-5: 1; flake TiO 2 2 the/Mxene is prepared by oxidizing and ultrasonically dispersing a layered MXene mixture; the layered MXene is prepared by carrying out microwave-assisted etching on MAX salt by using organic base; MOFs is prepared by hydrothermal synthesis of metal precursor salt and organic ligand. Also, the present invention disclosesA specific preparation method is disclosed. TiO 2 2 The catalytic material can efficiently remove nitrate in industrial wastewater under visible light and has high nitrogen selectivity under the synergistic catalytic action of a heterojunction structure catalytic main body formed by the catalytic material and MOFs and flaky MXene, and can be applied to the fields of industrial water treatment, photocatalysis and the like.
Description
Technical Field
The invention relates to the field of preparation of photocatalytic materials, in particular to TiO for removing nitrate radical 2 a/MXene/MOFs catalytic material and a preparation method thereof.
Background
Too high a nitrate content in wastewater can lead to eutrophication of lakes and rivers and to a series of health problems for human bodies. Therefore, the removal of nitrate from wastewater is a problem that needs to be solved urgently in various countries. The photocatalysis removal of nitrate has high removal efficiency and high nitrogen selectivity, and becomes a hotspot of research. In the photocatalytic material, TiO 2 The photocatalyst has the advantages of low price, no toxicity and good stability, and shows great potential in the photocatalysis process. However, TiO is only capable of producing UV response due to its fast recombination of electron-hole and wider band gap 2 Failing to be applied on a large scale. Therefore, it is an urgent problem to improve the activity of the photocatalytic material and to research the photocatalytic material capable of generating visible light response. By adding the cocatalyst or combining with other semiconductors to construct a heterojunction structure, the problem of high recombination rate of photo-generated electrons and holes can be effectively solved, so that the activity of the photocatalytic material is improved.
MXene is a new type of two-dimensional transition metal carbide or carbonitride prepared by etching a layer of aluminum of MAX. In the field of photocatalysis, MXene has many advantages and becomes a high-efficiency photocatalytic cocatalyst. First, MXene has hydrophilicity, which is beneficial to the adsorption of water molecules by the photocatalytic material, thereby promoting the reaction of photocatalysis to water. Second, MXene has a large number of hydrophilic functional groups on its surface that can bind to most semiconductor photocatalytic materials and produce strong interactions. In conclusion, MXene has good application prospect in photocatalysis. However, since MXene has very few applications in water treatment, it is becoming a new direction for future research to combine MXene as a promoter with a semiconductor to obtain a more efficient photocatalytic material.
The Metal Organic Framework (MOF) is formed by connecting organic ligands and metal ions or metal clusters through coordination bonds. MOFs have high porosity, large specific surface area and tunable pore channels. Due to the large specific surface area, MOFs can provide abundant reaction sites, promote charge separation through the effect of ligand-metal charge transfer, and reduce the intrinsic electric word pair-hole combination rate of the photocatalytic material. Also, as a semiconductor, MOFs also have visible light response. Therefore, MOFs show great application prospects in the field of photocatalysis.
Related patents have been reported for the photocatalytic removal of nitrate from wastewater. The patent CN101066795A utilizes nano zero-valent iron doped titanium dioxide to achieve the purpose of removing nitrate radicals in wastewater, but an ultraviolet lamp is adopted in the photocatalysis process, and no response is carried out in a visible light region; the patent CN111974385A prepares Ag/SiO 2 @cTiO 2 The core-shell structure achieves the effect of removing high-concentration nitrate under the condition of coexistence of high-concentration chloride ions, but the photocatalytic material still needs an ultraviolet lamp to achieve light activation and is lack of visible light interregional response; patent CN110227516B prepares ZnIn 2 S 4 /BiPO 4 The specific surface area and the pore volume of the material of the p-n heterojunction photocatalyst are obviously improved, and CuBi is prepared by patent CN110227517B 2 O 4 /BiPO 4 The p-n heterojunction photocatalyst effectively promotes the rapid separation of photo-generated electrons and holes, and although both the catalysts can be activated in a visible light range, the nitrate removal rate and the nitrogen selectivity of the catalysts are low.
In view of the above, the existing photocatalysts cannot meet the requirement of efficiently removing nitrate in wastewater, and the preparation of a catalyst capable of efficiently removing nitrate in response in a visible light region has been slow.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior art, the invention provides TiO for removing nitrate radical 2 A novel way for preparing flaky MXene is provided, and the TiO grows in situ on the surface of the prepared flaky MXene by using the MXene as a cocatalyst 2 So that TiO is present 2 The connection with the cocatalyst is more compact. Using a form of electrostatic assembly, the TiO is 2 The combination of/MXene and MOFs forms a heterojunction, promotes the rapid separation of photogenerated electrons and holes, solves the problem of high recombination rate of photogenerated electrons and holes of the traditional photocatalytic material, enables the photocatalyst to be excited in a visible light region, and improves the effective utilization rate of solar energy.
The technical scheme is as follows: the invention relates to a TiO 2 the/MXene/MOFs photocatalysis material is characterized in that: the material is sheet TiO 2 /MXene and MOFs crystal assembled electrostatically to form flaky TiO 2 The mass ratio of the/MXene to the MOFs crystal is 1-5: 1.
Wherein the flake TiO 2 the/Mxene is prepared by oxidizing and ultrasonically dispersing a layered MXene mixture; the layered MXene is prepared by organic base microwave-assisted etching of MAX salt; the MOFs is prepared by hydrothermal synthesis of metal precursor salt and organic ligand.
TiO 2 2 The preparation method of the/MXene/MOFs photocatalytic material is characterized by comprising the following steps: the method comprises the following steps:
1) flake TiO 2 2 Preparation of the/MXene mixture: 1-2 parts of MAX salt, 15-25 parts of MAX salt, 5-15 parts of MAX salt, organic alkali solution and H at room temperature 2 O 2 Uniformly mixing, performing microwave treatment at 600-1000W for 10-20 min, centrifuging, washing with deionized water with 5-10 times of the mass of the precipitate for 1-5 times, adding the washed precipitate and deionized water with 5-10 times of the mass of the precipitate into a reaction kettle, uniformly mixing, performing ultrasonic treatment at 600-1000W for 5-20 min, centrifuging, and taking supernatant to obtain flaky TiO 2 a/MXene mixture;
2) preparing MOFs crystals: adding 1-10 parts by mass of metal precursor salt, 10-50 parts by mass of organic ligand and an organic solvent into a hydrothermal reaction kettle at room temperature, uniformly mixing, reacting at 150-200 ℃ for 12-24 h, cooling to room temperature, centrifuging, washing with deionized water and ethanol with the mass of the solid being 3-5 times that of the solid for 3-5 times, and drying the solid at 60-80 ℃ for 5-12 h to obtain MOFs crystals;
3)TiO 2 preparation of/MXene/MOFs photocatalytic material: 1-5 parts of MOFs crystal and 5-25 parts of flaky TiO at room temperature 2 Adding the MXene mixture into a reaction kettle, uniformly mixing, carrying out electrostatic assembly for 20-60 min, centrifuging, washing the solid with deionized water and ethanol with the mass of 3-5 times that of the solid for 2-4 times, and drying at 50-70 ℃ for 10-15 h to obtain TiO 2 the/MXene/MOFs photocatalysis material.
Wherein, the MAX salt in the step 1) is Ti 2 AlC or Ti 3 AlC 2 (ii) a The organic base is lithium diisopropylamide or lithium hexamethyldisilazide; said H 2 O 2 The concentration of (A) is 30 wt% -50 wt%.
Wherein, the metal precursor salt in the step 2) is ferric chloride hexahydrate or ferric sulfate; the organic ligand is terephthalic acid or 2-amino terephthalic acid; the organic solvent is dimethyl sulfoxide or N, N-dimethylformamide.
The concentration of nitrate is measured by an ion meter, nitrite is measured by an N- (1-naphthyl) -amine spectrophotometry (GB13580.7-92), ammonia nitrogen is measured by a Nassner reagent spectrophotometry (HJ535-2009), and total nitrogen is detected by an alkaline potassium persulfate digestion ultraviolet spectrophotometry. The method for calculating the nitrate radical removal rate comprises the following steps:
R(NO 3 - )＝[C(NO 3 - ) 0 -C(NO 3 - ) t ]/C(NO 3 - ) 0
wherein R (NO) 3 - ) Representing the removal rate of nitrate radical, C (NO) 3 - ) 0 Representing the initial content of nitrate nitrogen, C (NO) 3 - ) t Represents after t time reactionThe content of nitrate nitrogen. N is a radical of 2 The calculation formula of selectivity is:
S(N 2 )＝[C(NO 3 - ) 0 -C(NO 2 - ) t -C(NH 4 + ) t -C(NO 3 - ) t ]/[C(NO 3 - ) 0 -C(NO 3 - ) t ]
wherein, S (N) 2 ) Represents N 2 Selectivity of (2), C (NO) 3 - ) 0 Representing the initial content of nitrate nitrogen, C (NO) 3 - ) t 、C(NO 2 - ) t 、C(NH 4 + ) t Representing the nitrate nitrogen content after the reaction at time t.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
1) a novel method for etching MXene is provided, wherein organic alkali is used as an etching agent and an intercalating agent, and the characteristic of high-efficiency heating of microwaves is utilized to etch Al to generate layered MXene salt. Compared with an HF etching method, the method for preparing MXene by combining microwave and organic base is more efficient, and the generated layered structure is more neat and uniform than the MXene layered structure generated by HF acid etching.
2) The organic alkali can be used as an etching agent and can also generate the effect of an intercalating agent, because molecules of the organic alkali can enter into MXene layers, so that the interlayer spacing between the MXene layers is enlarged, the intercalation agent is prevented from being additionally used, and the possibility is provided for preparing flaky MXene. In addition, MXene etched by alkali carries-OH functional groups, and compared with MXene carrying-F functional groups etched by a traditional HF etching method, the MXene has larger interlayer spacing, and flaky MXene is more convenient to prepare.
3) By means of H 2 O 2 As O 2 Source of oxidation of a portion of MXene to TiO 2 And can be added by controlling the addition of H 2 O 2 Amount of (D) and reaction time control to produce TiO 2 The amount of (c). Compared with MXene oxidation by a hydrothermal method and a calcining method, MXene oxidation by H 2 O 2 MXene can be oxidized in MXeneInternal face of (2) to form TiO 2 Instead of only forming TiO on the surface exposed to air 2 And utilizes H 2 O 2 Can oxidize flaky MXene, but the calcining method and the hydrothermal method cannot oxidize flaky MXene to generate TiO 2 . By in situ formation of TiO from MXene 2 Strengthen TiO 2 Association with the cocatalyst MXene to give TiO 2 The electrons on the catalyst can be more efficiently transferred to the catalyst MXene to improve the TiO 2 Activity of (2).
4) Flake TiO 2 2 and/MXene is assembled with MOFs to construct a heterojunction. Flake TiO 2 2 Layered TiO/MXene ratio 2 The MXene has more exposed reaction sites, utilizes the high specific surface area of MOFs and is TiO 2 the/MXene provides a large number of reactive active sites and avoids TiO 2 Agglomeration of/MXene enhances TiO 2 The activity of/MXene and the formation of heterojunction with MOFs with visible light response accelerate the separation of photo-generated charge and holes, thereby improving the activity of the photocatalytic material.
5) TiO prepared by the invention 2 Under the condition of illumination, TiO of/MXene/MOFs photocatalysis material 2 And the electrons in the valence bands of the MOFs are first photo-activated and migrate to their respective conduction bands, respectively, leaving holes. From the heterogeneous distribution of photogenerated electrons and holes, TiO is formed 2 The valence band points to the built-in electric field of the MOFs conduction band, and the electrons of the MOFs are transferred to TiO 2 In the valence band with a hole, TiO 2 The generated electrons are transferred to the cocatalyst MXene, so that the recombination of photogenerated electrons and holes is reduced, more photogenerated electrons participate in the reaction of reducing nitrate radicals, and the activity of the catalytic material is improved.
6) TiO prepared by the invention 2 the/MXene/MOFs photocatalysis material can remove over 90 percent of nitrate solution containing 500mgN/L under the condition of visible light and formic acid as a hole scavenger, and N is 2 The selectivity can reach 90 percent, is higher than the existing photocatalytic material which can remove nitrate under the condition of visible light, and has high N 2 And the photocatalyst is a high-efficiency visible light photocatalytic material.
Drawings
FIG. 1 is TiO 2 SEM image of/MXene/MOFs photocatalytic material;
FIG. 2 is TiO 2 And the performance diagram of the/MXene/MOFs photocatalysis material for removing nitrate.
Detailed Description
The technical solution of the present invention is further described with reference to the accompanying drawings and the detailed description.
Example 1:
TiO of this example 2 The preparation method of the/MXene/MOFs photocatalytic material comprises the following steps:
1) flake TiO 2 2 Preparation of the/MXene mixture: taking 1.2g of Ti at room temperature 3 AlC 2 21g of lithium diisopropylamide, 10g of 30% H 2 O 2 Mixing the solution, performing microwave treatment at 800W for 15min, centrifuging, washing with 5 times of deionized water, adding the washed precipitate and 5 times of deionized water into a reaction kettle, mixing, performing ultrasonic treatment at 800W for 15min, centrifuging, and collecting supernatant to obtain sheet TiO 2 a/MXene mixture;
2) preparing MOFs crystals: at room temperature, adding 2.7g of ferric chloride hexahydrate, 1.35g of terephthalic acid and 40g of N-N dimethylformamide into a hydrothermal reaction kettle according to the mass ratio of a metal precursor to an organic ligand of 2:1, uniformly mixing, reacting for 12 hours at 150 ℃, cooling to room temperature, centrifuging, respectively washing solids for 3 times by using deionized water and ethanol with the mass of 3 times that of the solids, and drying for 12 hours at 60 ℃ to obtain MOFs crystals;
3)TiO 2 preparation of/MXene/MOFs photocatalytic material: 1g of MOFs crystals and 5g of TiO at room temperature 2 Adding the/MXene mixture into a reaction kettle, uniformly mixing, performing electrostatic assembly for 60min, centrifuging, washing the solid with deionized water and ethanol with the mass of 3 times of that of the solid for 3 times, and drying at 70 ℃ for 15h to obtain TiO 2 the/MXene/MOFs photocatalysis material.
And (3) testing: weigh 200mL, 500mg N Nitrate radical solution of/L, adding TiO 2 the/MXene/MOFs photocatalytic material and 40mL/L formic acid solution are stirred for 30min in the dark to remove the nitrate radical adsorption effect. Then under the irradiation of a xenon lamp,taking a water sample every 30min, and measuring the contents of nitrate, ammonia nitrogen and nitrite in the water sample. Finally, after xenon lamp irradiation for 4 hours, the removal rate of nitrate reaches 95.5%, and the nitrogen selectivity reaches 96%. The change of the nitrogen-containing components in the water with time is shown in FIG. 2.
Example 2:
TiO of this example 2 The preparation method of the/MXene/MOFs photocatalytic material comprises the following steps:
1) flake TiO 2 2 Preparation of MXene mixture: taking 1.2g of Ti at room temperature 3 AlC 2 21g of lithium hexamethyldisilazide, 10g of 50% H 2 O 2 Mixing the solution, performing microwave treatment at 800W for 15min, centrifuging, washing with 5 times of deionized water, mixing the precipitate with 5 times of deionized water, ultrasonic treating at 800W for 15min, centrifuging, and collecting supernatant to obtain sheet TiO 2 a/MXene mixture;
2) preparing MOFs crystals: at room temperature, adding 2.7g of ferric chloride hexahydrate, 1.35g of terephthalic acid and 40g of N-N dimethylformamide into a hydrothermal reaction kettle according to the mass ratio of a metal precursor to an organic ligand of 2:1, uniformly mixing, reacting for 12 hours at 150 ℃, cooling to room temperature, centrifuging, respectively washing solids for 3 times by using deionized water and ethanol with the mass of 3 times that of the solids, and drying for 12 hours at 60 ℃ to obtain MOFs crystals;
3)TiO 2 preparation of/MXene/MOFs photocatalytic material: 1g of MOFs crystals and 5g of TiO at room temperature 2 Adding the/MXene mixture into a reaction kettle, uniformly mixing, performing electrostatic assembly for 60min, centrifuging, washing the solid with deionized water and ethanol with the mass of 3 times of that of the solid for 3 times, and drying at 70 ℃ for 15h to obtain TiO 2 the/MXene/MOFs photocatalysis material.
And (3) testing: weigh 200mL, 500mg N Nitrate radical solution of/L, adding TiO 2 the/MXene/MOFs photocatalytic material and 40mL/L formic acid solution are stirred for 30min in the dark to remove the nitrate radical adsorption effect. And then, under the irradiation of a xenon lamp, taking a water sample every 30min, and measuring the contents of nitrate, ammonia nitrogen and nitrite in the water sample. Finally, after 4 hours of xenon lamp irradiation, the removal rate of nitrate radical92.5 percent and 91 percent of nitrogen selectivity.
Example 3:
TiO of this example 2 The preparation method of the/MXene/MOFs photocatalytic material comprises the following steps:
1) flake TiO 2 2 Preparation of the/MXene mixture: taking 1.2g of Ti at room temperature 3 AlC 2 21g of lithium diisopropylamide, 10g of 50% H 2 O 2 Mixing the solution, performing microwave treatment at 900W for 18min, centrifuging, washing with 5 times of deionized water, adding the washed precipitate and 5 times of deionized water into a reaction kettle, mixing, performing ultrasonic treatment at 800W for 15min, centrifuging, and collecting supernatant to obtain sheet TiO 2 a/MXene mixture;
2) preparing MOFs crystals: at room temperature, adding 3.7g of ferric sulfate, 1.85g of terephthalic acid and 40g of N-N dimethylformamide into a hydrothermal reaction kettle according to the mass ratio of a metal precursor to an organic ligand of 2:1, uniformly mixing, reacting at 160 ℃ for 12 hours, cooling to room temperature, centrifuging, respectively washing solids for 3 times by using deionized water and ethanol with the mass of 3 times that of the solids, and drying at 60 ℃ for 12 hours to obtain MOFs crystals;
3)TiO 2 preparation of/MXene/MOFs photocatalytic material: 1g of MOFs crystals and 5g of TiO at room temperature 2 Adding the/MXene mixture into a reaction kettle, uniformly mixing, performing electrostatic assembly for 60min, centrifuging, washing the solid with deionized water and ethanol with the mass of 3 times of that of the solid for 3 times, and drying at 70 ℃ for 15h to obtain TiO 2 the/MXene/MOFs photocatalysis material.
And (3) testing: weigh 200mL, 500mg N Nitrate radical solution of/L, adding TiO 2 the/MXene/MOFs photocatalytic material and 40mL/L formic acid solution are stirred for 30min in the dark to remove the nitrate radical adsorption effect. And then, under the irradiation of a xenon lamp, taking a water sample every 30min, and measuring the contents of nitrate, ammonia nitrogen and nitrite in the water sample. Finally, after xenon lamp irradiation for 4 hours, the removal rate of nitrate reaches 90.7%, and the nitrogen selectivity reaches 92%.
Example 4:
TiO of this example 2 Preparation method of/MXene/MOFs photocatalytic material and packageThe method comprises the following steps:
1) flake TiO 2 2 Preparation of the/MXene mixture: taking 1.2g of Ti at room temperature 2 AlC, 20g of lithium diisopropylamide, 10g of 50% H 2 O 2 Mixing the solution, performing microwave treatment at 800W for 15min, centrifuging, washing with 5 times of deionized water, adding the washed precipitate and 5 times of deionized water into a reaction kettle, mixing, performing ultrasonic treatment at 800W for 15min, centrifuging, and collecting supernatant to obtain sheet TiO 2 a/MXene mixture;
2) preparing MOFs crystals: at room temperature, adding 2.7g of ferric chloride hexahydrate, 0.9g of terephthalic acid and 40g of N-N dimethylformamide into a hydrothermal reaction kettle according to the mass ratio of a metal precursor to an organic ligand of 3:1, uniformly mixing, reacting for 12 hours at 150 ℃, cooling to room temperature, centrifuging, respectively washing solids for 3 times by using deionized water and ethanol with the mass of 3 times that of the solids, and drying for 12 hours at 60 ℃ to obtain MOFs crystals;
3)TiO 2 preparation of/MXene/MOFs photocatalytic material: 1g of MOFs crystals and 5g of TiO at room temperature 2 Adding the/MXene mixture into a reaction kettle, uniformly mixing, performing electrostatic assembly for 60min, centrifuging, washing the solid with deionized water and ethanol with the mass of 3 times of that of the solid for 3 times, and drying at 70 ℃ for 15h to obtain TiO 2 the/MXene/MOFs photocatalysis material.
And (3) testing: weigh 200mL, 500mg N Nitrate radical solution of/L, adding TiO 2 the/MXene/MOFs photocatalytic material and 40mL/L formic acid solution are stirred for 30min in the dark to remove the nitrate radical adsorption effect. And then under the irradiation of a xenon lamp, taking a water sample every 30min, and measuring the contents of nitrate, ammonia nitrogen and nitrite in the water sample. Finally, after 4 hours of xenon lamp irradiation, the removal rate of nitrate reaches 90%, and the selectivity of nitrogen reaches 91.3%.
Example 5:
TiO of this example 2 The preparation method of the/MXene/MOFs photocatalytic material comprises the following steps:
1) flake TiO 2 2 Preparation of MXene mixture: taking 1.2g of Ti at room temperature 3 AlC 2 21g of lithium diisopropylamide, 10g of 30% H 2 O 2 Mixing the solution, performing microwave treatment at 800W for 15min, centrifuging, washing with 5 times of deionized water, adding the washed precipitate and 5 times of deionized water into a reaction kettle, mixing, performing ultrasonic treatment at 800W for 15min, centrifuging, and collecting supernatant to obtain sheet TiO 2 a/MXene mixture;
2) preparing MOFs crystals: at room temperature, adding 2.7g of ferric chloride hexahydrate, 1.35g of terephthalic acid and 40g of dimethyl sulfoxide into a hydrothermal reaction kettle according to the mass ratio of a metal precursor to an organic ligand of 2:1, uniformly mixing, reacting at 150 ℃ for 12 hours, cooling to room temperature, centrifuging, respectively cleaning the solid with deionized water and ethanol with the mass of 3 times that of the solid for 3 times, and drying at 60 ℃ for 12 hours to obtain MOFs crystals;
3)TiO 2 preparation of/MXene/MOFs photocatalytic material: 1g of MOFs crystals and 5g of TiO at room temperature 2 Adding the/MXene mixture into a reaction kettle, uniformly mixing, performing electrostatic assembly for 60min, centrifuging, washing the solid with deionized water and ethanol with the mass of 3 times of that of the solid for 3 times, and drying at 70 ℃ for 15h to obtain TiO 2 the/MXene/MOFs photocatalysis material.
And (3) testing: weigh 200mL, 500mg N Nitrate radical solution of/L, adding TiO 2 the/MXene/MOFs photocatalytic material and 40mL/L formic acid solution are stirred for 30min in the dark to remove the nitrate radical adsorption effect. And then, under the irradiation of a xenon lamp, taking a water sample every 30min, and measuring the contents of nitrate, ammonia nitrogen and nitrite in the water sample. Finally, after 4 hours of xenon lamp irradiation, the removal rate of nitrate reaches 93.5%, and the selectivity of nitrogen reaches 90.5%.
Claims (5)
1. TiO 2 2 the/MXene/MOFs photocatalysis material is characterized in that: the material is sheet TiO 2 /MXene and MOFs crystal are assembled electrostatically to form sheet TiO 2 The mass ratio of the/MXene to the MOFs crystal is 1-5: 1.
2. The TiO of claim 1 2 the/MXene/MOFs photocatalysis material is characterized in that: the flake TiO is 2 the/Mxene is prepared by oxidizing and ultrasonically dispersing a layered MXene mixture; the above-mentionedThe layered MXene is prepared by carrying out microwave-assisted etching on MAX salt by using organic base; the MOFs is prepared by hydrothermal synthesis of metal precursor salt and organic ligand.
3. TiO 2 2 The preparation method of the/MXene/MOFs photocatalytic material is characterized by comprising the following steps: the method comprises the following steps:
1) flake TiO 2 2 Preparation of the/MXene mixture: at room temperature, 1-2 parts by weight of MAX salt, 15-25 parts by weight of MAX salt, 5-15 parts by weight of MAX salt, organic alkali solution and H 2 O 2 Uniformly mixing, performing microwave treatment at 600-1000W for 10-20 min, centrifuging, washing with deionized water with 5-10 times of the mass of the precipitate for 1-5 times, adding the washed precipitate and deionized water with 5-10 times of the mass of the precipitate into a reaction kettle, uniformly mixing, performing ultrasonic treatment at 600-1000W for 5-20 min, centrifuging, and taking supernatant to obtain flaky TiO 2 a/MXene mixture;
2) preparing MOFs crystals: adding 1-10 parts by mass of metal precursor salt, 10-50 parts by mass of organic ligand and an organic solvent into a hydrothermal reaction kettle at room temperature, uniformly mixing, reacting at 150-200 ℃ for 12-24 h at a mass ratio of the metal precursor to the organic ligand of 2-5: 1, cooling to room temperature, centrifuging, washing with deionized water and ethanol with the mass of the solid being 3-5 times that of the solid for 3-5 times, and drying the solid at 60-80 ℃ for 5-12 h to obtain MOFs crystals;
3)TiO 2 preparation of/MXene/MOFs photocatalytic material: 1-5 parts of MOFs crystal and 5-25 parts of flaky TiO respectively by mass at room temperature 2 Adding the/MXene mixture into a reaction kettle, uniformly mixing, performing electrostatic assembly for 20-60 min, centrifuging, washing the solid with deionized water and ethanol which are 3-5 times of the mass of the solid for 2-4 times, and drying at 50-70 ℃ for 10-15 h to obtain TiO 2 The material is/MXene/MOFs photocatalysis material.
4. The TiO of claim 3 2 The preparation method of the/MXene/MOFs photocatalytic material is characterized by comprising the following steps: the MAX salt in the step 1) is Ti 2 AlC or Ti 3 AlC 2 (ii) a The organic base is lithium diisopropylamide or lithium hexamethyldisilazide;said H 2 O 2 The concentration of (A) is 30 wt% -50 wt%.
5. The TiO of claim 3 2 The preparation method of the/MXene/MOFs photocatalytic material is characterized by comprising the following steps: the metal precursor salt in the step 2) is ferric chloride hexahydrate or ferric sulfate; the organic ligand is terephthalic acid or 2-amino terephthalic acid; the organic solvent is dimethyl sulfoxide or N, N-dimethylformamide.
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| CN115430444A (en) * | 2022-09-29 | 2022-12-06 | 北京林业大学 | Method for degrading macrolide antibiotic wastewater by using MXenes/NZVI catalyst in cooperation with photoactivated persulfate |
| CN115779939A (en) * | 2022-12-05 | 2023-03-14 | 河南科技学院 | Rare earth doped copper bismuthate/MXene composite material, preparation method and application thereof in photocatalysis nitrogen fixation |
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| CN109746011A (en) * | 2018-12-10 | 2019-05-14 | 济南大学 | Composite photo-catalyst derived from a kind of MOF base and preparation method thereof |
| CN111841592A (en) * | 2020-08-17 | 2020-10-30 | 盐城工学院 | In-situ derivatization synthesis of TiO by using Ti-based MOF2-Ti3C2Tx composite photocatalyst and application thereof |
| CN112251193A (en) * | 2020-09-25 | 2021-01-22 | 同济大学 | Composite wave-absorbing material based on MXene and metal organic framework and preparation method and application thereof |
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| CN109746011A (en) * | 2018-12-10 | 2019-05-14 | 济南大学 | Composite photo-catalyst derived from a kind of MOF base and preparation method thereof |
| CN111841592A (en) * | 2020-08-17 | 2020-10-30 | 盐城工学院 | In-situ derivatization synthesis of TiO by using Ti-based MOF2-Ti3C2Tx composite photocatalyst and application thereof |
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| CN115779939A (en) * | 2022-12-05 | 2023-03-14 | 河南科技学院 | Rare earth doped copper bismuthate/MXene composite material, preparation method and application thereof in photocatalysis nitrogen fixation |
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