CN116328843A - Heterogeneous photocatalyst and preparation method and application thereof - Google Patents
Heterogeneous photocatalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN116328843A CN116328843A CN202211718761.1A CN202211718761A CN116328843A CN 116328843 A CN116328843 A CN 116328843A CN 202211718761 A CN202211718761 A CN 202211718761A CN 116328843 A CN116328843 A CN 116328843A
- Authority
- CN
- China
- Prior art keywords
- solution
- bivo
- mil
- heterogeneous
- powder
- 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.)
- Pending
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000013206 MIL-53 Substances 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 30
- 229920005610 lignin Polymers 0.000 claims abstract description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 57
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 14
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 14
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 239000012456 homogeneous solution Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 238000000926 separation method Methods 0.000 abstract description 17
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000012546 transfer Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/16—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
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Abstract
The invention belongs to the technical field of photocatalysis, and in particular relates to a heterogeneous photocatalyst which is prepared from MIL-53 (Fe) powder and BiVO 4 The solution is prepared, wherein the content of MIL-53 (Fe) powder is 5% -20% by mass, biVO 4 The solution was added to 100%. The invention also discloses a preparation method of the heterogeneous photocatalyst, which comprises the following specific steps: MIL-53 (Fe) powder was added to BiVO 4 In the solution, after hydrothermal reaction, cooling to room temperature, centrifuging, washing and drying to obtain the required MIL-53 (Fe)/BiVO 4 Heterogeneous photocatalysts. The invention also discloses application of the heterogeneous photocatalyst in lignin catalysis. The heterogeneous photocatalyst provided by the invention has strong oxidation-reduction capability and strong charge separation capability, and realizes high-selectivity directional conversion of lignin.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a heterogeneous photocatalyst, and a preparation method and application thereof.
Background
Lignin is taken as a global first large aromatic natural renewable resource, lignin has great potential for producing chemicals such as aromatic hydrocarbon, phenol and the like, and only lignin is taken as industrial waste for treatment, so that environmental pollution can be caused while resources are wasted, and if depolymerization of lignin can be realized, the shortage problem of fossil resources such as petroleum and the like can be relieved, waste can be changed into valuables, and environmental pollution caused by burning and the like can be reduced. Lignin, therefore, has great potential as a largest renewable carbon resource to replace fossil resources to produce high value chemicals, especially organic oxygenates. However, lignin conversion pathways are diverse and selectivity is difficult to control, and is a great challenge in the field of biomass utilization. The photocatalysis can realize high-selectivity chemical conversion under mild conditions, and the high-value utilization of the photocatalysis lignin has been developed into an emerging research field in recent years. However, the existing photocatalysis technology also has some technical problems to be solved urgently: traditional photocatalysts such as TiO 2 The rapid recombination of photo-generated electron-hole pairs results in a low quantum yield of the photocatalyst. Therefore, development and utilization of the construction of heterojunction photocatalysts have been the focus of research in the field of photocatalysis.
The bismuth-based material has the advantages of dispersed valence band energy level, narrow band gap, high carrier mobility and the like, has excellent performance in various fields of photocatalysis, but the application of the bismuth-based material in the field of photocatalysis is limited by the low visible light utilization rate and fast composite photogenerated carrier. Therefore, further improvement of the activity of bismuth-based photocatalysts has become a current research focus. Although the conventional heterojunction photocatalyst can realize effective interface transfer and space separation of electron holes under the condition of light excitation, the heterojunction still has some fundamental problems, which directly affect the practical application (Chem, 2020,6,1543-1559). From the thermodynamic point of view, the photo-generated electron hole separation efficiency is at the cost of reducing the oxidation capability of two semiconductor photocatalysts, while most lignin-related molecular conversion processes are redox processes, which require a certain oxidation-reduction potential to drive, thus being unfavorable for lightCatalytic reactions occur. From a kinetic perspective, the existence of photo-generated electron holes in the original photocatalyst can inhibit the interfacial transfer of electron holes in other catalysts due to the existence of electrostatic interactions. Inspired by the principle of photosynthesis of plants in nature, the novel direct Z-shaped heterojunction composite photocatalytic material attracts the eyes of researchers (chem., 2020,6:1-15;Angew Chem.Int.Ed.Engl, 2017,56,2684-8; chem. Eng. J.,2017,325.690-699.) and the Z-shaped heterojunction can realize the spatial separation of redox sites, and ensure that a photocatalyst can keep a proper valence conduction band position, so that stronger redox reaction capacity is kept. Therefore, the Bi-based Z-type heterojunction catalyst is very likely to become a novel high-efficiency photocatalyst capable of realizing high-selectivity directional conversion of lignin. BiVO (BiVO) 4 As a promising photocatalyst, attention is being paid to the photocatalyst (Angew.chem.int.Ed.Engl.2019, 58 (32), 10873-10878) because of its inherent advantages of non-toxicity, high chemical stability and high utilization, however, pure BiVO 4 The performance in lignin photocatalytic reactions is still unsatisfactory because of its high conduction band potential and rapid charge recombination (2019, adv, mate, 31 (20), e 1806938).
Thus, how to BiVO 4 Modification to increase BiVO 4 Photocatalytic performance in lignin reactions becomes very necessary.
Disclosure of Invention
The invention aims to solve the technical problems and provide a heterogeneous photocatalyst which has strong oxidation-reduction capability and strong charge separation capability and realizes high-selectivity directional conversion of lignin.
The technical scheme of the invention is as follows:
a heterogeneous photocatalyst is prepared from MIL-53 (Fe) powder and BiVO 4 The solution is prepared, wherein the content of MIL-53 (Fe) powder is 5% -20% by mass, biVO 4 The solution was added to 100%.
The Metal Organic Framework (MOF) of the invention is composed of organic ligand and metal ion or metal cluster through coordination bond, can provide a large amount of required specific surface area, and is realized by ion and metal charge transferMIL-53 (Fe) can respond in visible light due to the existence of ferrite clusters and can induce electrons on MIL-53 (Fe) Fe-O clusters to flow from O 2- Transfer to Fe 3+ Accelerating the transfer of charge. In addition, MIL-53 (Fe) has larger specific surface area and chemical stability in organic solvent, so the invention modifies BiVO by MIL-53 (Fe) powder 4 The solution, the heterogeneous photocatalyst obtained has strong oxidation-reduction capability and strong charge separation capability, and the high-selectivity directional conversion of lignin is realized.
Preferably, the preparation method of MIL-53 (Fe) powder comprises the following steps: terephthalic acid and FeCl 3 ·6H 2 O is dissolved in N, N-dimethylformamide under magnetic stirring to form a homogeneous solution, and after hydrothermal reaction, the solution is cooled to room temperature, centrifuged, washed and dried to obtain MIL-53 (Fe) powder.
Preferably, the terephthalic acid and FeCl of the invention 3 ·6H 2 The molar ratio of O to N, N-dimethylformamide is 1:1:180-280.
Preferably, the present invention is carried out at 100-160℃for 10-16h of hydrothermal reaction.
Preferably, the BiVO of the invention 4 The preparation method of the solution comprises the following steps: bi (NO) 3 ) 3 ·5H 2 Dissolving O and carboxymethyl cellulose in 1.0-2.0mol/L dilute nitric acid solution, adding dilute sodium hydroxide solution containing 5.0mmol ammonium metavanadate and having a concentration of 1.0-2.0mol/L until the pH of the mixed solution is neutral, to obtain BiVO 4 A solution.
Preferably, the Bi (NO) 3 ) 3 ·5H 2 O, carboxymethyl cellulose and dilute nitric acid solution in the mass ratio of 5:6:4-6.
Preferably, the present invention adds MIL-53 (Fe) powder to BiVO 4 In the solution, after hydrothermal reaction, cooling to room temperature, centrifuging, washing and drying to obtain MIL-53 (Fe)/BiVO 4 Heterogeneous photocatalysts.
Preferably, the present invention performs the hydrothermal reaction at 140-180℃for 18-24 hours.
Use of the heterogeneous photocatalyst of the present invention in lignin catalysis, said heterogeneous photocatalystThe catalyst has depolymerization effect on lignin model and real lignin, and is used for modifying BiVO by MIL-53 (Fe) 4 The solution can obviously improve lignin conversion rate and selectivity.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the heterogeneous photocatalyst obtained by the invention has strong oxidation-reduction capability and strong charge separation capability, and realizes high-selectivity directional conversion of lignin.
2. MIL-53 (Fe)/BiVO of the invention 4 The two phases are fully interwoven together, so that the strong reducing capability of MIL-53 (Fe) and BiVO can be effectively reserved 4 Strong oxidizing ability and effectively separates electron-hole generated by the catalyst itself due to ultraviolet-visible light excitation, MIL-53 (Fe)/BiVO 4 Heterogeneous photocatalyst shows a higher purity than pure phase BiVO 4 More excellent photocatalytic performance.
3. When the heterogeneous photocatalyst obtained by the invention is used for photocatalytic lignin model objects and real lignin, lignin molecules can be solved into aromatic compounds with higher value under the condition of room temperature, and the heterogeneous photocatalyst has higher selectivity.
4. The preparation method of the heterogeneous photocatalyst is simple, the preparation condition is mild, the operation is convenient, and the industrial scale-up production is convenient.
Drawings
FIG. 1 shows MIL-53 (Fe)/BiVO prepared in example 1 according to the present invention 4 Heterogeneous photocatalyst XRD pattern.
FIG. 2 shows MIL-53 (Fe)/BiVO according to the present invention 4 A graph of the charge separation mechanism in a heterojunction.
Detailed Description
The following detailed description of embodiments of the invention, it being understood that the embodiments described in this application are exemplary and intended to be illustrative of the invention and not to be construed as limiting the invention.
Example 1
A method for preparing a heterogeneous photocatalyst, comprising the steps of:
(1) Preparation of MIL-53 (Fe) powder: at room temperature, paraxylylene is addedAcid and FeCl 3 ·6H 2 O is dissolved in N, N-dimethylformamide under magnetic stirring to form a homogeneous solution, the homogeneous solution is subjected to hydrothermal reaction at 100 ℃ for 10 hours, cooled to room temperature, subjected to centrifugal separation at 7000r/min, the obtained solid is alternately washed for 3 times by distilled water and deionized water, and dried at constant temperature for 24 hours in an air atmosphere at 60 ℃ to obtain MIL-53 (Fe) powder, wherein terephthalic acid and FeCl are obtained 3 ·6H 2 The molar ratio of O to N, N-dimethylformamide is 1:1:240, a step of;
(2)BiVO 4 preparation of the solution: bi (NO) 3 ) 3 ·5H 2 Dissolving O and carboxymethyl cellulose in 2.0mol/L dilute nitric acid solution, slowly adding 5.0mmol ammonium metavanadate and 1.5mol/L dilute sodium hydroxide solution until the pH of the mixed solution is neutral to obtain BiVO 4 Solutions in which Bi (NO 3 ) 3 ·5H 2 The mass ratio of O to carboxymethyl cellulose to dilute nitric acid solution is 5:6:5;
(3) Heterogeneous photocatalyst preparation: MIL-53 (Fe) powder was added to BiVO 4 In the solution, the hydrothermal reaction time is 18h at 140 ℃, the solution is cooled to room temperature, 6000r/min is centrifugally separated, the obtained solid is alternately washed for 3 times by distilled water and deionized water, and is dried for 24h at constant temperature in an air atmosphere at 60 ℃ to obtain MIL-53 (Fe)/BiVO 4 The XRD pattern of the heterogeneous photocatalyst is shown in figure 1, and XRD diffraction peaks of the sample correspond to BiVO respectively 4 (JCPDS No. 14-140688) diffraction patterns, located at 18.6 degrees, 28.8 degrees, 30.5 degrees and 35.1 degrees, respectively corresponding to monoclinic phase BiVO 4 The (100), (-121) (040) (002) and (051) crystal planes, which also demonstrate MIL-53 (Fe)/BiVO 4 The catalyst has better crystallinity, mainly BiVO 4 Wherein MIL-53 (Fe)/BiVO 4 The charge separation mechanism in the heterojunction is shown in fig. 2.
Example 2
A method for preparing a heterogeneous photocatalyst, comprising the steps of:
(1) Preparation of MIL-53 (Fe) powder: terephthalic acid and FeCl under room temperature conditions 3 ·6H 2 O is dissolved in N, N-dimethylformamide under magnetic stirring to form homogeneous solution, the hydrothermal reaction time is 16h at 100 ℃, and the solution is cooled to room temperature of 7000r/min centrifugal separation, washing the obtained solid with distilled water and deionized water alternately for 3 times, and drying at constant temperature in air atmosphere at 80deg.C for 10 hr to obtain MIL-53 (Fe) powder, wherein the terephthalic acid and FeCl are 3 ·6H 2 The molar ratio of O to N, N-dimethylformamide is 1:1:180;
(2)BiVO 4 preparation of the solution: bi (NO) 3 ) 3 ·5H 2 Dissolving O and carboxymethyl cellulose in 1.5mol/L dilute nitric acid solution, slowly adding 5.0mmol ammonium metavanadate and 1.5mol/L dilute sodium hydroxide solution until the pH of the mixed solution is neutral to obtain BiVO 4 Solutions in which Bi (NO 3 ) 3 ·5H 2 The mass ratio of O to carboxymethyl cellulose to dilute nitric acid solution is 5:6:4;
(3) Heterogeneous photocatalyst preparation: MIL-53 (Fe) powder was added to BiVO 4 In the solution, the hydrothermal reaction time is 24 hours at 140 ℃, the solution is cooled to room temperature, 7000r/min centrifugal separation is carried out, the obtained solid is alternately washed for 3 times by distilled water and deionized water, and the solid is dried for 10 hours at constant temperature in an air atmosphere at 100 ℃ to obtain MIL-53 (Fe)/BiVO 4 Heterogeneous photocatalysts.
Example 3
A method for preparing a heterogeneous photocatalyst, comprising the steps of:
(1) Preparation of MIL-53 (Fe) powder: terephthalic acid and FeCl under room temperature conditions 3 ·6H 2 O is dissolved in N, N-dimethylformamide under magnetic stirring to form a homogeneous solution, the homogeneous solution is subjected to hydrothermal reaction at 160 ℃ for 10 hours, cooled to room temperature, centrifugally separated at 8000r/min, the obtained solid is alternately washed for 3 times by distilled water and deionized water, and is dried at constant temperature for 24 hours in an air atmosphere at 60 ℃ to obtain MIL-53 (Fe) powder, wherein terephthalic acid and FeCl are obtained by the steps of 3 ·6H 2 The molar ratio of O to N, N-dimethylformamide is 1:1:240, a step of;
(2)BiVO 4 preparation of the solution: bi (NO) 3 ) 3 ·5H 2 Dissolving O and carboxymethyl cellulose in 1.0mol/L dilute nitric acid solution, slowly adding dilute sodium hydroxide solution containing 5.0mmol ammonium metavanadate and concentration of 2.0mol/L until pH of the mixed solution is neutral to obtainTo BiVO 4 Solutions in which Bi (NO 3 ) 3 ·5H 2 The mass ratio of O to carboxymethyl cellulose to dilute nitric acid solution is 5:6:6;
(3) Heterogeneous photocatalyst preparation: MIL-53 (Fe) powder was added to BiVO 4 In the solution, the hydrothermal reaction time is 24 hours at 180 ℃, the solution is cooled to room temperature, 8000r/min centrifugal separation is carried out, the obtained solid is alternately washed for 3 times by distilled water and deionized water, and the solid is dried for 24 hours at constant temperature in an air atmosphere at 60 ℃ to obtain MIL-53 (Fe)/BiVO 4 Heterogeneous photocatalysts.
Example 4
A method for preparing a heterogeneous photocatalyst, comprising the steps of:
(1) Preparation of MIL-53 (Fe) powder: terephthalic acid and FeCl under room temperature conditions 3 ·6H 2 O is dissolved in N, N-dimethylformamide under magnetic stirring to form a homogeneous solution, the homogeneous solution is subjected to hydrothermal reaction at 160 ℃ for 10 hours, cooled to room temperature, subjected to centrifugal separation at 7000r/min, the obtained solid is alternately washed for 3 times by distilled water and deionized water, and dried at constant temperature for 16 hours in an air atmosphere at 70 ℃ to obtain MIL-53 (Fe) powder, wherein terephthalic acid and FeCl are obtained 3 ·6H 2 The mass ratio of O to N, N-dimethylformamide is 1:1:280;
(2)BiVO 4 preparation of the solution: bi (NO) 3 ) 3 ·5H 2 Dissolving O and carboxymethyl cellulose in 1.5mol/L dilute nitric acid solution, slowly adding 5.0mmol ammonium metavanadate and 1.5mol/L dilute sodium hydroxide solution until the pH of the mixed solution is neutral to obtain BiVO 4 Solutions in which Bi (NO 3 ) 3 ·5H 2 The molar ratio of O to carboxymethyl cellulose to dilute nitric acid solution is 5:6:5;
(3) Heterogeneous photocatalyst preparation: MIL-53 (Fe) powder was added to BiVO 4 In the solution, the hydrothermal reaction time is 24 hours at 180 ℃, the solution is cooled to room temperature, 7000r/min centrifugal separation is carried out, the obtained solid is alternately washed for 3 times by distilled water and deionized water, and the solid is dried for 16 hours at constant temperature in an air atmosphere at 80 ℃ to obtain MIL-53 (Fe)/BiVO 4 Heterogeneous photocatalysts.
Comparative example 1
Pure BiVO 4 The preparation method of the photocatalyst comprises the following steps: bi (NO) 3 ) 3 ·5H 2 Dissolving O and carboxymethyl cellulose in 2.0mol/L dilute nitric acid solution, slowly adding dilute sodium hydroxide solution containing 5.0mmol ammonium metavanadate and having a concentration of 1.5mol/L until the pH of the mixed solution is neutral, performing hydrothermal reaction for 20 hours at 180 ℃, cooling to room temperature, performing centrifugal separation at 6000r/min, alternately washing the obtained solid with distilled water and deionized water for 3 times, and performing constant-temperature drying in an air atmosphere at 60 ℃ for 24 hours to obtain BiVO 4 Solutions in which Bi (NO 3 ) 3 ·5H 2 The mass ratio of O to carboxymethyl cellulose to dilute nitric acid solution is 5:6:5.
Comparative example 2
Example 1 was repeated except that MIL-53 (Fe) powder was added in different amounts (see Table 1).
Comparative example 3
Example 1 was repeated except that MIL-53 (Fe) powder was added in different amounts (see Table 1).
Example 5
The reaction selects a typical lignin model substance (2-phenoxy 1-acetophenone) as a reaction substrate. The method comprises the following specific steps: 100mg of the catalysts prepared according to the preparation methods described in examples 1 to 4 and comparative examples 1 to 3 and according to the corresponding examples in Table 1 were, respectively, degassed under vacuum and then dispersed by ultrasound into 5mL of acetonitrile solution containing 0.1mmol of 2-phenoxy 1-acetophenone. Oxygen is introduced into the whole reactor before the light test to keep the whole reaction device in an oxygen-full state, and the pressure of the reactor is kept at 0.1MPa. The above mixture was dispersed by ultrasound and the sample was kept in suspension under a magnetic stirrer. After 30min of dark adsorption, the lamp was turned on, the experiment was terminated after 8h of reaction, the catalyst was removed from the liquid phase product with a 0.22 μm organic filter membrane, and the reaction was detected by gas chromatography (Agilent 1680, fid).
TABLE 1MIL-53 (Fe)/BiVO 4 Results of evaluation of Activity of heterogeneous photocatalyst
As can be seen from Table 1, the present invention modifies BiVO by MIL-53 (Fe) 4 The solution can obviously improve the lignin conversion rate and selectivity, but BiVO which is not modified by MIL-53 (Fe) 4 As can be seen from the data of comparative examples 2 and 3, when the solution is used for catalyzing lignin conversion, the conversion rate is lower and the selectivity is weaker, and when the mass percent of MIL-53 (Fe) powder is higher than 20% or lower than 5%, the conversion rate and the selectivity of the modified catalyst are obviously reduced, which means that the addition amount of MIL-53 (Fe) powder is within the scope of the invention, and the modified BiVO 4 The catalyst prepared by the solution has strong oxidation-reduction capability and strong charge separation capability, and realizes the high-selectivity directional conversion of lignin.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A heterogeneous photocatalyst, characterized by: from MIL-53 (Fe) powder and BiVO 4 The solution is prepared, wherein the content of MIL-53 (Fe) powder is 5% -20% by mass, biVO 4 The solution was added to 100%.
2. The heterogeneous photocatalyst of claim 1, wherein: the preparation method of the MIL-53 (Fe) powder comprises the following steps of: terephthalic acid and FeCl 3 ·6H 2 O is dissolved in N, N-dimethylformamide under magnetic stirring to form a homogeneous solution, and after hydrothermal reaction, the solution is cooled to room temperature, centrifuged, washed and dried to obtain MIL-53 (Fe) powder.
3. The heterogeneous photocatalyst of claim 2, wherein: the terephthalic acid, feCl 3 ·6H 2 The molar ratio of O to N, N-dimethylformamide is 1:1:180-280.
4. The heterogeneous photocatalyst of claim 2, wherein: carrying out hydrothermal reaction at 100-160 ℃ for 10-16h.
5. The heterogeneous photocatalyst of claim 1, wherein the BiVO 4 The preparation method of the solution comprises the following steps: bi (NO) 3 ) 3 ·5H 2 Dissolving O and carboxymethyl cellulose in 1.0-2.0mol/L dilute nitric acid solution, adding dilute sodium hydroxide solution containing 5.0mmol ammonium metavanadate and having a concentration of 1.0-2.0mol/L until the pH of the mixed solution is neutral, to obtain BiVO 4 A solution.
6. The heterogeneous photocatalyst of claim 5, wherein: the Bi (NO) 3 ) 3 ·5H 2 The mass ratio of O to carboxymethyl cellulose to dilute nitric acid solution is 5:6:4-6.
7. The method for preparing a heterogeneous photocatalyst according to any one of claims 1 to 6, wherein the specific steps are as follows: MIL-53 (Fe) powder was added to BiVO 4 In the solution, after hydrothermal reaction, cooling to room temperature, centrifuging, washing and drying to obtain MIL-53 (Fe)/BiVO 4 Heterogeneous photocatalysts.
8. The method for preparing heterogeneous photocatalyst according to claim 7, wherein: carrying out hydrothermal reaction at 140-180 ℃ for 18-24h.
9. Use of a heterogeneous photocatalyst according to any one of claims 1-6 in lignin catalysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211718761.1A CN116328843A (en) | 2022-12-29 | 2022-12-29 | Heterogeneous photocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211718761.1A CN116328843A (en) | 2022-12-29 | 2022-12-29 | Heterogeneous photocatalyst and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116328843A true CN116328843A (en) | 2023-06-27 |
Family
ID=86881067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211718761.1A Pending CN116328843A (en) | 2022-12-29 | 2022-12-29 | Heterogeneous photocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116328843A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004202335A (en) * | 2002-12-25 | 2004-07-22 | Sk Kaken Co Ltd | Photocatalyst compound powder having visible light responsiveness |
| CN108554458A (en) * | 2018-05-29 | 2018-09-21 | 江苏海川卓越密封材料有限公司 | Core/membranous type composite bismuth vanadium photocatalyst and preparation method thereof |
| CN110465285A (en) * | 2019-07-29 | 2019-11-19 | 江苏大学 | A kind of BiVO4The preparation method and application of@carbon nano dot composite photocatalyst material |
| US20200179916A1 (en) * | 2017-04-28 | 2020-06-11 | Cambridge Enterprise Limited | Composite Metal Organic Framework Materials, Processes for Their Manufacture and Uses Thereof |
| CN114405520A (en) * | 2022-01-26 | 2022-04-29 | 中国矿业大学 | Ternary composite photocatalyst containing heteropoly acid and preparation method and application thereof |
| CN114985015A (en) * | 2022-06-30 | 2022-09-02 | 华南理工大学 | NH 2 -MIL-53(Fe)/Ag@g-C 3 N 4 photo-Fenton catalyst and preparation method and application thereof |
| CN115283015A (en) * | 2022-07-08 | 2022-11-04 | 重庆大学 | Organic metal framework composite photocatalyst BiVO 4 @NH 2 Process for producing (E) -MIL-125 (Ti) |
| CN115318295A (en) * | 2022-08-08 | 2022-11-11 | 东南大学 | Catalyst for photocatalytic depolymerization of lignin beta-O-4 ketone model compound and preparation method thereof |
-
2022
- 2022-12-29 CN CN202211718761.1A patent/CN116328843A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004202335A (en) * | 2002-12-25 | 2004-07-22 | Sk Kaken Co Ltd | Photocatalyst compound powder having visible light responsiveness |
| US20200179916A1 (en) * | 2017-04-28 | 2020-06-11 | Cambridge Enterprise Limited | Composite Metal Organic Framework Materials, Processes for Their Manufacture and Uses Thereof |
| CN108554458A (en) * | 2018-05-29 | 2018-09-21 | 江苏海川卓越密封材料有限公司 | Core/membranous type composite bismuth vanadium photocatalyst and preparation method thereof |
| CN110465285A (en) * | 2019-07-29 | 2019-11-19 | 江苏大学 | A kind of BiVO4The preparation method and application of@carbon nano dot composite photocatalyst material |
| CN114405520A (en) * | 2022-01-26 | 2022-04-29 | 中国矿业大学 | Ternary composite photocatalyst containing heteropoly acid and preparation method and application thereof |
| CN114985015A (en) * | 2022-06-30 | 2022-09-02 | 华南理工大学 | NH 2 -MIL-53(Fe)/Ag@g-C 3 N 4 photo-Fenton catalyst and preparation method and application thereof |
| CN115283015A (en) * | 2022-07-08 | 2022-11-04 | 重庆大学 | Organic metal framework composite photocatalyst BiVO 4 @NH 2 Process for producing (E) -MIL-125 (Ti) |
| CN115318295A (en) * | 2022-08-08 | 2022-11-11 | 东南大学 | Catalyst for photocatalytic depolymerization of lignin beta-O-4 ketone model compound and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| DANDAN WANG ET AL.: "Optimized design of BiVO4/NH2-MIL-53(Fe) heterostructure for enhanced photocatalytic degradation of methylene blue and ciprofloxacin under visible light", 《JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS》, vol. 154, 4 March 2021 (2021-03-04), pages 2 * |
| 翟勃银等: "BiVO4/MOF 复合材料的合成及其光催化性能", 《燃料化学学报》, vol. 47, no. 4, 30 April 2019 (2019-04-30), pages 2 - 3 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107456991B (en) | g-C3N4Preparation method of quantum dot supported bismuth tungstate nanosheet photocatalyst | |
| CN105170186A (en) | Preparation method of core-shell structure BiOX@MTL(Fe) photocatalyst | |
| CN108686665B (en) | Preparation method of nanorod zinc ferrite in-situ composite lamellar titanium dioxide photocatalytic material | |
| CN108126756A (en) | Bismuth tungstate-MIL-53 (Al) composite material, preparation method and application | |
| Deng et al. | Nanomaterial-based photocatalytic hydrogen production | |
| CN103357424A (en) | Photocatalyst for selective oxidation of toluene and toluene derivatives | |
| Wang et al. | Construction of indium oxide/N-doped titanium dioxide hybrid photocatalysts for efficient and selective oxidation of cyclohexane to cyclohexanone | |
| Liang et al. | Synthesis and structure of a bismuth-cobalt bimetal coordination polymer for green efficient photocatalytic degradation of organic wastes under visible light | |
| CN112892608A (en) | Water-stable composite material for photodegradation of organic pollutants and preparation method thereof | |
| CN111330602A (en) | Carbon cloth loaded BiOCl/BiVO4Recyclable flexible composite photocatalytic material, preparation method and application | |
| WO2023108950A1 (en) | PREPARATION METHOD FOR Z-SCHEME α-FE2O3/ZNIN2S4 COMPOSITE PHOTOCATALYST AND USE THEREOF | |
| Zheng et al. | Fabrication of Z-scheme WO3/KNbO3 photocatalyst with enhanced separation of charge carriers | |
| Li et al. | Synthesis of Ni 12 P 5 on Co 3 S 4 material for effectively improved photocatalytic hydrogen production from water splitting under visible light | |
| CN111185199A (en) | Z-type heterojunction photocatalyst and preparation method and application thereof | |
| Ge et al. | Efficient visible-light-driven selective conversion of glucose to high-value chemicals over Bi2WO6/Co-thioporphyrazine composite in aqueous media | |
| CN105435816B (en) | A kind of CdXZn1‑XS nanowire composite photocatalysts and preparation method and applications | |
| CN113976148A (en) | Z-shaped C60/Bi/BiOBr composite photocatalyst and preparation method and application thereof | |
| CN112495436A (en) | Polypyrrole/titanium dioxide/graphite phase carbon nitride ternary composite photocatalytic material and preparation method thereof | |
| CN111672523A (en) | Three-dimensional ZnFe2O4/BiOCl (001) composite photocatalyst and preparation method thereof | |
| CN116328843A (en) | Heterogeneous photocatalyst and preparation method and application thereof | |
| CN117138802A (en) | Bi (Bi) 2 MoO 6 @ZnIn 2 S 4 Hierarchical S-shaped heterostructure photocatalyst and preparation method thereof | |
| CN115814782A (en) | BiVO 4 Preparation method of base-pressure electro-optic catalytic composite nano material | |
| CN108970604A (en) | A kind of molybdenum vanadium niobium base composite oxidate and its synthetic method and application | |
| CN113351202A (en) | Titanium dioxide/ruthenium monoatomic noble metal nano catalytic material for degrading pollutants and preparation method thereof | |
| CN112892607A (en) | Stable ternary composite material for preparing hydrogen by photocatalytic water decomposition and preparation method 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 |