CN113522367A - Preparation method and preparation method of nano silver chromate modified MOFs photocatalyst - Google Patents
Preparation method and preparation method of nano silver chromate modified MOFs photocatalyst Download PDFInfo
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- CN113522367A CN113522367A CN202110661575.8A CN202110661575A CN113522367A CN 113522367 A CN113522367 A CN 113522367A CN 202110661575 A CN202110661575 A CN 202110661575A CN 113522367 A CN113522367 A CN 113522367A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 76
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 43
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003446 ligand Substances 0.000 claims abstract description 23
- 239000013110 organic ligand Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 22
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 20
- SATWKVZGMWCXOJ-UHFFFAOYSA-N 4-[3,5-bis(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=CC(C=2C=CC(=CC=2)C(O)=O)=C1 SATWKVZGMWCXOJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 238000004729 solvothermal method Methods 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000004480 active ingredient Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 9
- 150000002603 lanthanum Chemical class 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- DHMGMTYGCBZFST-UHFFFAOYSA-N dibismuth;dioxido(dioxo)chromium Chemical compound [Bi+3].[Bi+3].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O DHMGMTYGCBZFST-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 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
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000003595 spectral effect Effects 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- OJKANDGLELGDHV-UHFFFAOYSA-N disilver;dioxido(dioxo)chromium Chemical compound [Ag+].[Ag+].[O-][Cr]([O-])(=O)=O OJKANDGLELGDHV-UHFFFAOYSA-N 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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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
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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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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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
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Abstract
The invention discloses a preparation method and application of a nano silver chromate modified MOFs photocatalyst, wherein the MOFs material is a Laval-Hill framework material, trimesic acid, 1,3, 5-tri (4-carboxyphenyl) benzene are used as organic ligands, and Fe is used as an active ingredient3+、La3+、Co2+The MOFs material is prepared by adopting a solvothermal method as an inorganic ligand, and then the nano silver chromate catalyst is loaded, and the method comprises the following steps: s1: preparing an inorganic ligand solution; s2: preparation of organic ligandsA solution; s3: preparing MOFs materials; s4: adding the obtained MOFs material into 0.05mol/L K2CrO4Soaking and adsorbing the solution for 0.5 to 3 hours, and dripping 0.1mol/L AgNO3And (3) stirring the solution at room temperature of 25 ℃ for reaction for 1-6 h, filtering, washing and drying to obtain the catalyst. The photocatalyst disclosed by the invention can be used for efficiently separating photoproduction electrons and holes, remarkably improving the photocatalytic reduction capability, having a wide spectral response range on visible light, and effectively improving the absorption rate and the effective utilization rate of sunlight.
Description
Technical Field
The invention belongs to the field of synthesis of functional MOFs materials, and particularly relates to a preparation method and a preparation method of a nano silver chromate modified MOFs photocatalyst.
Background
The metal-organic framework material is a novel porous material with a periodic multi-dimensional network structure formed by self-assembly of transition metal ions and carboxylic acids or nitrogen-containing organic polydentate ligands through coordination, and has the advantages of high porosity, low density, large specific surface area, regular pore channels, adjustable pore diameter, diversity of topological structure, tailorability and the like. The MOFs material has the characteristics of both inorganic material rigidity and organic material flexibility, has important application in gas storage, catalysts, separation, adsorption and photoelectric magnetic materials, and has high molecular selectivity due to a large number of unsaturated metal sites. Application of MOFs to photocatalytic reduction of CO2Renewable hydrocarbon or alcohol is synthesized to replace fossil fuel, so that carbon recycling is realized, and the energy crisis of the earth is reduced. In CO2In the process of photocatalytic reduction, MOFs provides a large number of active sites for reactants, and meanwhile, the multi-channel structure is more favorable for charge and proton transportation. Currently, MOFs are used to photo-catalyze CO2The reduction for preparing renewable fuel still has the following problems: (1) the conjugated system with larger MOFs causes the separation efficiency of photo-generated electron and hole pairs to be low, and the photo-generated electron and hole pairs are easy to combine, so that the photo-catalytic activity is low; (2) most MOFs have wide forbidden band widths Eg between a semiconductor and an insulator, narrow response spectrum to visible light and low utilization rate of the visible light.
In order to solve the problems, the invention uses trimesic acid and 1,3, 5-tri (4-carboxyphenyl) benzene as organic ligands as dual organic ligands for the first time, and uses Fe3+、La3+、Co2+Preparing a novel Laval Hill framework material for an inorganic ligand by adopting a solvothermal method, growing nano silver chromate in situ, and embedding the nano silver chromate into the MOFs framework structure; the invention realizes the compounding of the nano silver chromate and the Laval framework material by utilizing a chemical precipitation method, and the different Fermi levels of the nano silver chromate and the Laval framework material form different formsThe structure of the mass junction changes the transmission path of electrons, so that the photoproduction electrons are spontaneously transferred from the crystal face of the nano silver chromate to the conduction band of the MOFs, the photoproduction electrons and holes are efficiently separated, the photoproduction electrons are accumulated on the MOFs, and the photocatalytic reduction capability is obviously improved; meanwhile, the forbidden band width of the nano silver chromate is only 1.6-1.7eV, the spectral response range of the nano silver chromate to visible light is wide, and the nano silver chromate is compounded with MOFs materials, so that the sunlight absorption rate and the effective utilization rate of the nano silver chromate can be effectively improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method and a preparation method of a nano silver chromate modified MOFs photocatalyst.
The technical scheme of the invention is summarized as follows:
a preparation method of a nano silver chromate modified MOFs photocatalyst is characterized in that the MOFs material is a Laval-Hill framework material, trimesic acid, 1,3, 5-tri (4-carboxyphenyl) benzene are used as organic ligands, and Fe is used as an active ingredient3+、La3+、Co2+The MOFs material is prepared by adopting a solvothermal method as an inorganic ligand, and then the nano silver chromate catalyst is loaded, and the method comprises the following steps:
s1: adding ferric salt, lanthanum salt and cobalt salt into 75% ethanol solution by volume fraction, stirring and dissolving at 50 ℃ to obtain inorganic ligand solution;
s2: dissolving trimesic acid and 1,3, 5-tri (4-carboxyphenyl) benzene in DMF to obtain an organic ligand solution;
s3: uniformly mixing an inorganic ligand solution and an organic ligand solution according to an equal volume ratio, transferring the mixture into a reaction kettle, stirring and reacting for 12-36 hours at 100-160 ℃ under a solvothermal condition, cooling to room temperature, centrifuging, washing and drying to obtain the MOFs material;
s4: adding the obtained MOFs material into 0.05mol/L K2CrO4Soaking and adsorbing the solution for 0.5 to 3 hours, and dripping 0.1mol/L AgNO3And (3) stirring the solution at the room temperature of 25 ℃ for reaction for 1-6 h, filtering, washing and drying to obtain the nano bismuth chromate/MOFs composite material.
Preferably, the iron salt is one or more of ferric nitrate, ferric acetate, ferric chloride and ferric sulfate.
Preferably, the lanthanum salt is one or more of lanthanum nitrate, lanthanum acetate, lanthanum chloride and lanthanum sulfate.
Preferably, the cobalt salt is one or more of cobalt nitrate, cobalt acetate, cobalt chloride and cobalt sulfate.
Preferably, the dosage ratio of the ferric salt, the lanthanum salt, the cobalt salt and the ethanol solution is (1-3) mmol: (0.5-1) mmol: (1.5-3.5) mmol: 10 mL.
Preferably, the dosage ratio of the trimesic acid, the 1,3, 5-tri (4-carboxyphenyl) benzene and the DMF is 1 mmol: (1-3) mmol: 10 mL.
Preferably, said MOFs material, K2CrO4Solution, AgNO3The dosage ratio of the solution is 1 g: (6-10) mL: (6-10) mL.
Nano silver chromate modified MOFs photocatalyst in CO2Application in photocatalytic reduction.
The invention has the beneficial effects that:
the invention uses trimesic acid and 1,3, 5-tri (4-carboxyl phenyl) benzene as organic ligands as dual organic ligands for the first time, and uses Fe3+、La3+、Co2+Preparing a novel Laval Hill framework material for an inorganic ligand by adopting a solvothermal method, growing nano silver chromate in situ, and embedding the nano silver chromate into the MOFs framework structure; the invention realizes the compounding of the nano silver chromate and the Laval framework material by utilizing a chemical precipitation method, and a heterojunction structure is formed due to different Fermi levels of the nano silver chromate and the Laval framework material, so that the transmission path of electrons is changed, the photoproduction electrons are spontaneously transferred from the crystal face of the nano silver chromate to the conduction band of the MOFs, the photoproduction electrons and holes are efficiently separated, the photoproduction electrons are accumulated on the MOFs, the photocatalytic reduction capability is obviously improved, and the CO-based photocatalytic reduction capability of the photoproduction electrons is improved2Photocatalytic reduction performance; MOFs have developed pore channel structures and high specific area, provide sufficient growth sites for silver chromate, avoid agglomeration among nano silver chromate particles and keep good surface effect and quantum size; meanwhile, the forbidden bandwidth of the nano silver chromate is only 1.6-1.7eV, the spectral response range of the nano silver chromate to visible light is wide, and the nano silver chromate is compounded with MOFs materials, so that the solar light resistance of the nano silver chromate to sunlight can be effectively improvedAbsorption rate and effective utilization rate.
Drawings
FIG. 1 is a flow chart of a preparation method of a nano silver chromate modified MOFs photocatalyst.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
The invention provides a preparation method of a nano silver chromate modified MOFs photocatalyst, which is provided by the embodiment of the invention, wherein the MOFs material is a Laval-Hill framework material, trimesic acid, 1,3, 5-tri (4-carboxyphenyl) benzene are used as organic ligands, and Fe is used as an active ingredient3+、La3+、Co2+The MOFs material is prepared by adopting a solvothermal method as an inorganic ligand, and then the nano silver chromate catalyst is loaded, and the method comprises the following steps:
s1: adding ferric salt, lanthanum salt and cobalt salt into 75% ethanol solution by volume fraction, stirring and dissolving at 50 ℃ to obtain inorganic ligand solution; the dosage ratio of the ferric salt, the lanthanum salt, the cobalt salt and the ethanol solution is (1-3) mmol: (0.5-1) mmol: (1.5-3.5) mmol: 10 mL; the ferric salt is one or more of ferric nitrate, ferric acetate, ferric chloride and ferric sulfate; the lanthanum salt is one or more of lanthanum nitrate, lanthanum acetate, lanthanum chloride and lanthanum sulfate; the cobalt salt is one or more of cobalt nitrate, cobalt acetate, cobalt chloride and cobalt sulfate;
s2: dissolving trimesic acid and 1,3, 5-tri (4-carboxyphenyl) benzene in DMF to obtain an organic ligand solution; the dosage ratio of the trimesic acid, the 1,3, 5-tri (4-carboxyphenyl) benzene and the DMF is 1 mmol: (1-3) mmol: 10 mL;
s3: uniformly mixing an inorganic ligand solution and an organic ligand solution according to an equal volume ratio, transferring the mixture into a reaction kettle, stirring and reacting for 12-36 hours at 100-160 ℃ under a solvothermal condition, cooling to room temperature, centrifuging, washing and drying to obtain the MOFs material;
s4: adding the obtained MOFs material into 0.05mol/L K2CrO4Soaking and adsorbing the solution for 0.5 to 3 hours, and dripping 0.1mol/L AgNO3Stirring the solution at room temperature of 25 ℃ for reaction for 1-6 h, and filteringFiltering, washing and drying to obtain the nano bismuth chromate/MOFs composite material; said MOFs material, K2CrO4Solution, AgNO3The dosage ratio of the solution is 1 g: (6-10) mL: (6-10) mL.
The invention further provides the application of the nano silver chromate modified MOFs photocatalyst in CO2Application in photocatalytic reduction.
Example 1
A preparation method of a nano silver chromate modified MOFs photocatalyst comprises the following steps:
s1: adding 2mmol of ferric nitrate, 1mmol of lanthanum nitrate and 3mmol of cobalt nitrate into 20mL of 75% ethanol solution by volume fraction, and stirring and dissolving at 50 ℃ to obtain an inorganic ligand solution;
s2: dissolving 2mmol of trimesic acid and 2mmol of 1,3, 5-tri (4-carboxyphenyl) benzene in 20mL of DMF to obtain an organic ligand solution;
s3: uniformly mixing 20mL of inorganic ligand solution and 20mL of organic ligand solution, transferring the mixture into a reaction kettle, stirring and reacting for 24 hours at 100 ℃ under the solvothermal condition, cooling to room temperature, centrifuging, washing and drying to obtain the MOFs material;
s4: 1g of MOFs was added to 6mL of 0.05mol/L K2CrO4Soaking and adsorbing in the solution for 0.5h, and dropwise adding 6mL of 0.1mol/L AgNO3And (3) stirring the solution at the room temperature of 25 ℃ for reaction for 1h, filtering, washing and drying to obtain the nano bismuth chromate/MOFs composite material.
Example 2
A preparation method of a nano silver chromate modified MOFs photocatalyst comprises the following steps:
s1: adding 4mmol of iron acetate, 1.5mmol of lanthanum acetate and 5mmol of cobalt acetate into 20mL of 75% ethanol solution by volume fraction, and stirring and dissolving at 50 ℃ to obtain an inorganic ligand solution;
s2: dissolving 2mmol of trimesic acid and 4mmol of 1,3, 5-tri (4-carboxyphenyl) benzene in 20mL of DMF to obtain an organic ligand solution;
s3: uniformly mixing 20mL of inorganic ligand solution and 20mL of organic ligand solution, transferring the mixture into a reaction kettle, stirring and reacting for 30 hours at the temperature of 130 ℃ under the solvothermal condition, cooling to room temperature, centrifuging, washing and drying to obtain the MOFs material;
s4: 1g of MOFs was added to 8mL of 0.05mol/L K2CrO4Soaking and adsorbing the solution for 0.5 to 3 hours, and dripping 8mL of 0.1mol/L AgNO3And (3) stirring the solution at the room temperature of 25 ℃ for reaction for 4 hours, filtering, washing and drying to obtain the nano bismuth chromate/MOFs composite material.
Example 3
A preparation method of a nano silver chromate modified MOFs photocatalyst comprises the following steps:
s1: adding 6mmol of ferric chloride, 2mmol of lanthanum chloride and 7mmol of cobalt chloride into 20mL of 75% ethanol solution by volume fraction, and stirring and dissolving at 50 ℃ to obtain an inorganic ligand solution;
s2: dissolving 2mmol of trimesic acid and 6mmol of 1,3, 5-tri (4-carboxyphenyl) benzene in 20mL of DMF to obtain an organic ligand solution;
s3: uniformly mixing 20mL of inorganic ligand solution and 20mL of organic ligand solution, transferring the mixture into a reaction kettle, stirring and reacting for 36 hours at 160 ℃ under the solvothermal condition, cooling to room temperature, centrifuging, washing and drying to obtain the MOFs material;
s4: 1g of MOFs was added to 10mL of 0.05mol/L K2CrO4Soaking and adsorbing in the solution for 3h, and dropwise adding 10mL of 0.1mol/L AgNO3And (3) stirring the solution at the room temperature of 25 ℃ for reaction for 6 hours, filtering, washing and drying to obtain the nano bismuth chromate/MOFs composite material.
The comparative example is MOFs material, and the preparation method comprises the following steps:
s1: adding 2mmol of ferric nitrate, 1mmol of lanthanum nitrate and 3mmol of cobalt nitrate into 20mL of 75% ethanol solution by volume fraction, and stirring and dissolving at 50 ℃ to obtain an inorganic ligand solution;
s2: dissolving 2mmol of trimesic acid and 2mmol of 1,3, 5-tri (4-carboxyphenyl) benzene in 20mL of DMF to obtain an organic ligand solution;
s3: and (2) uniformly mixing 20mL of inorganic ligand solution and 20mL of organic ligand solution, transferring the mixture into a reaction kettle, stirring and reacting for 24 hours at 100 ℃ under the solvothermal condition, cooling to room temperature, centrifuging, washing and drying to obtain the MOFs material.
The photocatalysts prepared in examples 1-3 and comparative example are respectively adopted to catalyze CO2Reduction to prepare alcohols, the test method is as follows:
adding 100mL of deionized water into a glass reactor, adding 0.5g of photocatalyst, and continuously introducing CO into the reactor at a flow rate of 150mL/min2CO to Water2Reaching saturation state, stirring uniformly, and introducing CO at constant flow of 50mL/min2Turning on a 500W xenon lamp source, allowing visible light with a wavelength of more than 420nm to pass through by using an optical filter, irradiating the visible light into a reaction system, reacting for 3h, collecting a liquid phase product, performing centrifugal separation, and performing qualitative and quantitative analysis by GC-MS and GC.
The following table shows the photocatalyst prepared in examples 1-3 and comparative example to CO2Catalytic reduction effect:
| example 1 | Example 2 | Example 3 | Comparative example | |
| Total alcohol yield/mmol/g-cat | 10.5 | 11.3 | 10.9 | 3.1 |
| Methanol selectivity/% | 52.7 | 56.4 | 57.1 | 50.2 |
| Ethanol selectivity/%) | 31.4 | 32.8 | 33.5 | 28.6 |
As can be seen from the above table, the total alcohol yield is much higher for examples 1-3 than for the comparative example, which illustrates that the photocatalysts prepared in examples 1-3 have a higher CO content2The catalytic reduction capability is far better than that of the comparative example.
Examples 1 to 3 first use trimesic acid and 1,3, 5-tris (4-carboxyphenyl) benzene as organic ligands, and Fe as a diorganoligand3+、La3+、Co2+Preparing a novel Laval Hill framework material for an inorganic ligand by adopting a solvothermal method, growing nano silver chromate in situ, and embedding the nano silver chromate into the MOFs framework structure; the invention realizes the compounding of the nano silver chromate and the Laval framework material by utilizing a chemical precipitation method, and a heterojunction structure is formed due to different Fermi levels of the nano silver chromate and the Laval framework material, so that the transmission path of electrons is changed, the photoproduction electrons are spontaneously transferred from the crystal face of the nano silver chromate to the conduction band of the MOFs, the photoproduction electrons and holes are efficiently separated, the photoproduction electrons are accumulated on the MOFs, the photocatalytic reduction capability is obviously improved, and the CO-based photocatalytic reduction capability of the photoproduction electrons is improved2Photocatalytic reduction performance; MOFs have developed pore channel structures and high specific area, provide sufficient growth sites for silver chromate, avoid agglomeration among nano silver chromate particles and keep good surface effect and quantum size; meanwhile, the forbidden band width of the nano silver chromate is only 1.6-1.7eV, the spectral response range of the nano silver chromate to visible light is wide, and the nano silver chromate is compounded with MOFs materials, so that the sunlight absorption rate and the sunlight absorption rate of the nano silver chromate can be effectively improvedThe effective utilization rate.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (8)
1. A preparation method of a nano silver chromate modified MOFs photocatalyst is characterized in that the MOFs material is a Laval-Hill framework material, trimesic acid, 1,3, 5-tri (4-carboxyphenyl) benzene are used as organic ligands, and Fe is used as an active ingredient3+、La3+、Co2+The MOFs material is prepared by adopting a solvothermal method as an inorganic ligand, and then the nano silver chromate catalyst is loaded, and the method comprises the following steps:
s1: adding ferric salt, lanthanum salt and cobalt salt into 75% ethanol solution by volume fraction, stirring and dissolving at 50 ℃ to obtain inorganic ligand solution;
s2: dissolving trimesic acid and 1,3, 5-tri (4-carboxyphenyl) benzene in DMF to obtain an organic ligand solution;
s3: uniformly mixing an inorganic ligand solution and an organic ligand solution according to an equal volume ratio, transferring the mixture into a reaction kettle, stirring and reacting for 12-36 hours at 100-160 ℃ under a solvothermal condition, cooling to room temperature, centrifuging, washing and drying to obtain the MOFs material;
s4: adding the obtained MOFs material into 0.05mol/L K2CrO4Soaking and adsorbing the solution for 0.5 to 3 hours, and dripping 0.1mol/L AgNO3And (3) stirring the solution at the room temperature of 25 ℃ for reaction for 1-6 h, filtering, washing and drying to obtain the nano bismuth chromate/MOFs composite material.
2. The method for preparing the nano silver chromate modified MOFs photocatalyst according to claim 1, wherein the iron salt is one or more of ferric nitrate, ferric acetate, ferric chloride and ferric sulfate.
3. The method for preparing the nano silver chromate modified MOFs photocatalyst according to claim 1, wherein the lanthanum salt is one or more of lanthanum nitrate, lanthanum acetate, lanthanum chloride and lanthanum sulfate.
4. The method for preparing the nano silver chromate modified MOFs photocatalyst according to claim 1, wherein the cobalt salt is one or more of cobalt nitrate, cobalt acetate, cobalt chloride and cobalt sulfate.
5. The method for preparing the nano silver chromate modified MOFs photocatalyst according to claim 1, wherein the dosage ratio of the iron salt, the lanthanum salt, the cobalt salt and the ethanol solution is (1-3) mmol: (0.5-1) mmol: (1.5-3.5) mmol: 10 mL.
6. The method for preparing the nano silver chromate modified MOFs photocatalyst according to claim 1, wherein the dosage ratio of the trimesic acid, the 1,3, 5-tris (4-carboxyphenyl) benzene and the DMF is 1 mmol: (1-3) mmol: 10 mL.
7. The method for preparing the MOFs photocatalyst modified by nano silver chromate according to claim 1, wherein the MOFs material K2CrO4Solution, AgNO3The dosage ratio of the solution is 1 g: (6-10) mL: (6-10) mL.
8. The method of using the nano silver chromate modified MOFs photocatalyst as claimed in any one of claims 1 to 7 in CO2Application in photocatalytic reduction.
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| CN114849782A (en) * | 2022-05-19 | 2022-08-05 | 江南大学 | Stepped Bi-MOF-M/CdS/Bi 2 S 3 Heterojunction visible-light-driven photocatalyst and preparation method thereof |
| CN115870005A (en) * | 2022-10-24 | 2023-03-31 | 蚌埠学院 | Ag 2 CrO 4 /UiO-66-NH 2 Composite photocatalyst, preparation method and photocatalytic application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114849782A (en) * | 2022-05-19 | 2022-08-05 | 江南大学 | Stepped Bi-MOF-M/CdS/Bi 2 S 3 Heterojunction visible-light-driven photocatalyst and preparation method thereof |
| CN114849782B (en) * | 2022-05-19 | 2023-03-24 | 江南大学 | Stepped Bi-MOF-M/CdS/Bi 2 S 3 Heterojunction visible-light-driven photocatalyst and preparation method thereof |
| CN115870005A (en) * | 2022-10-24 | 2023-03-31 | 蚌埠学院 | Ag 2 CrO 4 /UiO-66-NH 2 Composite photocatalyst, preparation method and photocatalytic application thereof |
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