CN114950439B - High-efficiency photolysis water hydrogen production MOF TiO 2 NiO material and preparation method and application thereof - Google Patents
High-efficiency photolysis water hydrogen production MOF TiO 2 NiO material and preparation method and application thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000001257 hydrogen Substances 0.000 title claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000006303 photolysis reaction Methods 0.000 title abstract description 7
- 230000015843 photosynthesis, light reaction Effects 0.000 title abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 75
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 49
- 239000008367 deionised water Substances 0.000 claims description 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 33
- 239000011941 photocatalyst Substances 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 23
- 239000007795 chemical reaction product Substances 0.000 claims description 20
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 12
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 70
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 6
- 239000013110 organic ligand Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000013086 titanium-based metal-organic framework Substances 0.000 abstract description 2
- 150000002816 nickel compounds Chemical class 0.000 abstract 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 74
- 230000001699 photocatalysis Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 13
- 239000011521 glass Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000005086 pumping Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000004523 catalytic cracking Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/39—
-
- B01J35/394—
-
- B01J35/613—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a high-efficiency photolysis water hydrogen production MOF TiO 2 -NiO materials, methods of making and uses thereof. Nickel compounds are widely used as hydrogen-producing catalyst for decomposing water, and by utilizing the characteristic that metal nickel ions are easy to coordinate with amino groups contained in organic ligands of metal organic framework materials and the characteristic that MOFs structure-function are adjustable, titanium-based MOF Ti-ATA is selected as a precursor material, and Ni is loaded in a high-dispersion manner 2+ And then calcining to obtain MOF TiO with high dispersity of promoter NiO, small particle size of material, large specific surface area and high surface hydrophilicity, thereby efficiently photolyzing water to produce hydrogen 2 -NiO material. The preparation method is simple, has wide sources of reaction raw materials, is easy to operate in experimental steps, has universality and potential design research value, and can be produced in batches.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, in particular to the technical field of photocatalytic decomposition of water to produce hydrogen, and relates to high-efficiency photocatalytic decomposition of water to produce hydrogen MOF TiO 2 -NiO materials, methods of making and uses thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The photocatalysis technology is widely focused at home and abroad due to the potential application of the photocatalysis technology in solving the problems of energy shortage, environmental pollution and the like. Hydrogen is a carbon-free green clean energy source. In recent years, with the increasing severity of the problem of energy shortage, the photocatalytic water splitting for hydrogen production attracts more and more attention. The cocatalyst can reduce the overpotential of the photocatalytic reaction and promote the separation of carriers in the reaction process, and is widely used in the field of photocatalytic water splitting, and the high-dispersion supported cocatalyst can greatly improve the catalytic efficiency.
DioxygenTitanium oxide (TiO) 2 ) Is a high-efficiency photocatalyst, has the performance of cracking water, and how to improve the efficiency of the photocatalyst for decomposing water into hydrogen is always a direction of attention of vast scientific researchers. Nickel-based compounds have been used in large amounts as promoters to increase the hydrogen production activity of the photocatalyst, nickel oxide (NiO) can be used as a hydrogen production promoter, and how to highly disperse the supported NiO is critical to increase the hydrogen production activity of the photocatalyst. The metal organic framework Materials (MOFs) are composed of metal ions and organic ligands, can be used as precursor materials for preparing traditional inorganic semiconductor photocatalysts, and the framework structure and the organic-inorganic composition of the metal organic framework materials are also conducive to loading the metal ions with high dispersibility.
Disclosure of Invention
The invention uses the characteristic that metal nickel ions are easy to coordinate with amino groups contained in organic ligands of metal organic framework materials, uses the characteristic that MOFs structure-function is adjustable, selects titanium-based MOF Ti-ATA as a precursor material, and loads Ni in a highly dispersed way 2+ And then calcining to obtain MOF TiO with high dispersity of promoter NiO, small particle size of material, large specific surface area and high surface hydrophilicity, thereby efficiently photolyzing water to produce hydrogen 2 -NiO material.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide the high-efficiency photolytic aquatic hydrogen MOF TiO 2 -NiO materials, methods of making and uses thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
high-efficiency photolysis water hydrogen production MOF TiO 2 A process for the preparation of NiO materials, comprising,
preparation of Ti-ATA: dissolving 2-amino terephthalic acid in 40mL of mixed solvent of N, N-dimethylformamide and 10mL of methanol, adding isopropyl titanate, stirring at room temperature for 5min, and transferring into a reaction kettle; heating the reaction kettle in an oven, cooling to room temperature, filtering and washing the reaction product, and airing in the air at room temperature to obtain yellow powder which is Ti-ATA;
preparation of Ti-ATA-Ni: dissolving nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring for 24 hours at room temperature, sufficiently washing the surface of a precipitate after suction filtration, drying in an oven, and drying for a period of time to obtain a Ti-ATA-Ni photocatalyst sample;
preparation of MOF TiO 2 NiO: placing Ti-ATA-Ni solid powder in a ceramic crucible, calcining in a muffle furnace for a period of time, and cooling at room temperature to obtain MOF TiO 2 NiO photocatalyst samples.
Further, the preparation of Ti-ATA, wherein the addition amount of 2-amino terephthalic acid is 10 mmol-20 mmol, and the addition amount of isopropyl titanate is 6 mmol-15 mmol.
Further, the reaction kettle is a 100mL polytetrafluoroethylene reaction kettle.
Further, the temperature of the reaction kettle in the oven is 110 ℃ and the time is 72 hours.
Further, in the preparation of Ti-ATA, the washing is performed 3 times with N, N-dimethylformamide, methanol and absolute ethanol, respectively.
Further, the nickel nitrate is added in an amount of 0.02mmol to 0.1mmol.
Further, in the preparation of Ti-ATA-Ni, the washing is carried out 3 times by using deionized water and absolute ethyl alcohol respectively.
Further, the preparation of MOF TiO 2 -NiO, wherein the calcination temperature is 450-700 ℃ and the calcination time is 2h.
High-efficiency photolysis water prepared according to the method produces hydrogen MOF TiO 2 -NiO material.
The MOF TiO 2 Application of NiO material in photolysis of water to produce hydrogen, and hydrogen production rate under full light reaches 1396 mu mol.h -1 ·g -1 。
The invention has the beneficial effects that:
(1) The invention utilizes the-NH on the organic ligand in Ti-ATA 2 And Ni 2+ Complexing to realize high dispersion of nickel nitrate. The compound containing Ni2+ is a high-efficiency hydrogen-producing promoter, and has high catalytic efficiency; is a transitionMetals, which are easily complexed with groups such as amino groups; low cost, abundant reserves, no toxicity and easy obtainment.
(2) The method is different from the traditional sol-gel method for preparing TiO 2 Or preparing other metal-loaded photocatalytic materials by a traditional MOF method, wherein the obtained photocatalytic materials are mostly explained from the aspects of large specific surface area and porosity of MOF, but not from the aspects of analyzing the structure, components and bond formation of the MOF, according to the characteristics of adjustable structure and function, nickel ions are firstly complexed with amino groups contained in a ligand of the MOF material such as Ti-ATA to form bond, so that Ti-ATA-Ni with high nickel dispersion and even single dispersion is obtained, the MOF TiO2-NiO photocatalytic material obtained after calcination has larger specific surface area, smaller particles and higher dispersion degree of a supported NiO hydrogen-producing cocatalyst.
(3) The photocatalysis material prepared by the invention has better photocatalysis activity, and the hydrogen production rate under full illumination reaches 1396 mu mol.h -1 ·g -1 。
(4) The method for preparing the photocatalytic material has universal applicability and is not only suitable for Ni 2+ The same applies to other series of transition metal element ions; not only is suitable for Ti-ATA, but also is suitable for other products containing-NH 2 Organic ligands of (C) and MOFs and COFs materials.
(5) The preparation method of the photocatalytic material has the advantages of controllable conditions, controllable results, simple synthesis method and experimental steps, great guiding significance in practical application and great industrial value.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is an XRD pattern of the products Ti-ATA and Ti-ATA-Ni of example 1 of the invention.
FIG. 2 is a graph showing the time-yield of hydrogen produced by catalytic cracking of Ti-ATA-Ni under UV-visible total light for different initial mole percentages of Ni in example 1 of the present invention.
FIG. 3 shows MOF TiO products of different calcination temperatures in examples 1 to 6 according to the invention 2 Time-yield profile of NiO catalytic cracking of aqueous hydrogen under uv-vis plenoptic.
FIG. 4 shows MOF TiO prepared in example 4 of the present invention 2 Ni2p XPS spectrum of NiO.
FIG. 5 shows MOF TiO as prepared in example 4 of the present invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 XRD pattern of NiO.
FIG. 6 shows MOF TiO as prepared in example 4 of the present invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 Time-yield profile of NiO catalytic cracking of aqueous hydrogen under uv-vis plenoptic.
FIG. 7 shows MOF TiO as prepared in example 4 of the present invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 -FT-IR diagram of NiO.
FIG. 8 shows MOF TiO as prepared in example 4 of the present invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 N of NiO 2 Adsorption-desorption graph.
FIG. 9 shows MOF TiO prepared in example 4 of the present invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 PL spectra of NiO excitation at 310nm wavelength.
FIG. 10 shows MOF TiO as prepared in example 4 of the present invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 -TEM image of NiO.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Raw material reagents used in the invention: isopropyl titanate (Ti (OiPr) 4 ) 2-amino terephthalic acid (H) 2 ATA), N-dimethylformamide, methanol, absolute ethanol, nickel nitrate hexahydrate (Ni (NO) 3 ) 2 ·6H 2 O), deionized water. All drugs used were of analytical grade (a.r.) and were not further purified.
The glass system used in the present invention is a closed quartz photolytic reactor (PerfectLight) with internal ventilation and external illumination.
The method for detecting the content of generated hydrogen in the invention comprises the following steps: ar was used as a carrier gas and measured by a gas chromatograph (Shiweipx GC-7806).
The invention is further illustrated below with reference to examples.
Example 1
Preparation of Ti-ATA: 15.8mmol of 2-amino terephthalic acid is dissolved in 40mL of mixed solvent of N, N-dimethylformamide and 10mL of methanol, 9.7mmol of isopropyl titanate is added, and the mixture is stirred for 5min at room temperature and then transferred into a 100mL reaction kettle; heating the reaction kettle in a 110 ℃ oven for 72 hours, cooling to room temperature, filtering a reaction product, respectively washing the reaction product with N, N-dimethylformamide, methanol and absolute ethyl alcohol for 3 times, and then airing the reaction product in room temperature air to finally obtain yellow powder which is Ti-ATA;
preparation of Ti-ATA-Ni: dissolving 0.02mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, filtering, washing the surface of the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying in a 60 ℃ oven, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with an initial Ni molar ratio of 20%;
preparation of Ti-ATA-Ni: dissolving 0.05mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, filtering, washing the surface of the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying in a 60 ℃ oven, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 50%;
preparation of Ti-ATA-Ni: dissolving 0.055mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, filtering, washing the surface of the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying in a 60 ℃ oven, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with an initial Ni molar ratio of 55%;
preparation of Ti-ATA-Ni: dissolving 0.06mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, filtering, washing the surface of the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying in a 60 ℃ oven, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with initial Ni molar ratio of 60%;
preparation of Ti-ATA-Ni: dissolving 0.065mmol nickel nitrate in 100mL deionized water, adding 100mg Ti-ATA, stirring at room temperature, filtering, washing the surface of the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying in a 60 ℃ oven, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 65%;
preparation of Ti-ATA-Ni: dissolving 0.07mmol nickel nitrate in 100mL deionized water, adding 100mg Ti-ATA, stirring at room temperature, filtering, washing the surface of the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying in a 60 ℃ oven, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with an initial Ni molar ratio of 70%;
preparation of Ti-ATA-Ni: dissolving 0.08mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, filtering, washing the surface of the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying in a 60 ℃ oven, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 80%;
preparation of Ti-ATA-Ni: dissolving 0.09mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, filtering, washing the surface of the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying in a 60 ℃ oven, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 90%;
preparation of Ti-ATA-Ni: dissolving 0.1mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, filtering, washing the surface of the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying in a 60 ℃ oven, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 100%;
20mg of each Ti-ATA-Ni photocatalyst obtained, 6mL of sacrificial agent methanol and 24mL of deionized water are added into a sealed glass system, and the reaction is carried out after vacuum pumping for 30min, so that the hydrogen generated immediately is detected.
FIG. 1 shows XRD patterns of the products Ti-ATA and Ti-ATA-Ni, showing that the diffraction peak positions of the samples were unchanged after Ni addition, indicating that Ti-ATA-Ni maintains the original Ti-ATA MOF framework structure. FIG. 2 is a graph showing the time-yield of hydrogen production by catalytic cracking of various initial mole percentages of Ni in the presence of UV-visible total light, comparing the initial mole ratio of Ni to the optimum performance of Ti-ATA-Ni of 60%, so that the optimum Ti-ATA-60% Ni samples were used for calcination in both the present example and the following examples.
Preparation of MOF TiO 2 NiO: placing Ti-ATA-60% Ni solid powder into a ceramic crucible, calcining in a muffle furnace at 450 ℃ for 2h, and cooling at room temperature to obtain calcined MOF TiO at 450 DEG C 2 -NiO catalyst sample.
Taking the obtained MOF TiO 2 20mg of NiO photocatalyst, 6mL of sacrificial agent methanol and 24mL of deionized water are added into a sealed glass system, the reaction is carried out after vacuum pumping is carried out for 30min, and the hydrogen generated immediately is detected.
Example 2
Preparation of Ti-ATA: 15.8mmol of 2-amino terephthalic acid is dissolved in 40mL of mixed solvent of N, N-dimethylformamide and 10mL of methanol, 9.7mmol of isopropyl titanate is added, and the mixture is stirred for 5min at room temperature and then transferred into a 100mL reaction kettle; heating the reaction kettle in a 110 ℃ oven for 72 hours, cooling to room temperature, filtering a reaction product, respectively washing the reaction product with N, N-dimethylformamide, methanol and absolute ethyl alcohol for 3 times, and then airing the reaction product in room temperature air to finally obtain yellow powder which is Ti-ATA;
preparation of Ti-ATA-Ni: dissolving 0.06mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, filtering, washing the surface of the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying in a 60 ℃ oven, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with initial Ni molar ratio of 60%;
preparation of MOF TiO 2 NiO: placing Ti-ATA-60% Ni solid powder into a ceramic crucible, calcining in a muffle furnace at 500 ℃ for 2h, and cooling at room temperature to obtain 500 ℃ calcined MOF TiO 2 -NiO catalyst sample.
Taking the obtained MOF TiO 2 20mg of NiO photocatalyst, 6mL of sacrificial agent methanol and 24mL of deionized water are added into a sealed glass system, the reaction is carried out after vacuum pumping is carried out for 30min, and the hydrogen generated immediately is detected.
Example 3
Preparation of Ti-ATA: 15.8mmol of 2-amino terephthalic acid is dissolved in 40mL of mixed solvent of N, N-dimethylformamide and 10mL of methanol, 9.7mmol of isopropyl titanate is added, and the mixture is stirred for 5min at room temperature and then transferred into a 100mL reaction kettle; heating the reaction kettle in a 110 ℃ oven for 72 hours, cooling to room temperature, filtering a reaction product, respectively washing the reaction product with N, N-dimethylformamide, methanol and absolute ethyl alcohol for 3 times, and then airing the reaction product in room temperature air to finally obtain yellow powder which is Ti-ATA;
preparation of Ti-ATA-Ni: dissolving 0.06mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, filtering, washing the surface of the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying in a 60 ℃ oven, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with initial Ni molar ratio of 60%;
preparation of MOF TiO 2 NiO: placing Ti-ATA-60% Ni solid powder into a ceramic crucible, calcining in a muffle furnace at 550deg.C for 2 hrCooling at room temperature to obtain 550 ℃ calcined MOF TiO 2 -NiO catalyst sample.
Taking the obtained MOF TiO 2 20mg of NiO photocatalyst, 6mL of sacrificial agent methanol and 24mL of deionized water are added into a sealed glass system, the reaction is carried out after vacuum pumping is carried out for 30min, and the hydrogen generated immediately is detected.
Example 4
Preparation of Ti-ATA: 15.8mmol of 2-amino terephthalic acid is dissolved in 40mL of mixed solvent of N, N-dimethylformamide and 10mL of methanol, 9.7mmol of isopropyl titanate is added, and the mixture is stirred for 5min at room temperature and then transferred into a 100mL reaction kettle; heating the reaction kettle in a 110 ℃ oven for 72 hours, cooling to room temperature, filtering a reaction product, respectively washing the reaction product with N, N-dimethylformamide, methanol and absolute ethyl alcohol for 3 times, and then airing the reaction product in room temperature air to finally obtain yellow powder which is Ti-ATA;
preparation of Ti-ATA-Ni: dissolving 0.06mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, filtering, washing the surface of the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying in a 60 ℃ oven, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with initial Ni molar ratio of 60%;
preparation of MOF TiO 2 NiO: placing Ti-ATA-60% Ni solid powder into a ceramic crucible, calcining in a muffle furnace at 600 ℃ for 2h, and cooling at room temperature to obtain 600 ℃ calcined MOF TiO 2 -NiO catalyst sample.
Taking the obtained MOF TiO 2 20mg of NiO photocatalyst, 6mL of sacrificial agent methanol and 24mL of deionized water are added into a sealed glass system, the reaction is carried out after vacuum pumping is carried out for 30min, and the hydrogen generated immediately is detected.
Example 5
Preparation of Ti-ATA: 15.8mmol of 2-amino terephthalic acid is dissolved in 40mL of mixed solvent of N, N-dimethylformamide and 10mL of methanol, 9.7mmol of isopropyl titanate is added, and the mixture is stirred for 5min at room temperature and then transferred into a 100mL reaction kettle; heating the reaction kettle in a 110 ℃ oven for 72 hours, cooling to room temperature, filtering a reaction product, respectively washing the reaction product with N, N-dimethylformamide, methanol and absolute ethyl alcohol for 3 times, and then airing the reaction product in room temperature air to finally obtain yellow powder which is Ti-ATA;
preparation of Ti-ATA-Ni: dissolving 0.06mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, filtering, washing the surface of the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying in a 60 ℃ oven, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with initial Ni molar ratio of 60%;
preparation of MOF TiO 2 NiO: placing Ti-ATA-60% Ni solid powder into a ceramic crucible, calcining in a muffle furnace at 650 ℃ for 2h, and cooling at room temperature to obtain 650 ℃ calcined MOF TiO 2 -NiO catalyst sample.
Taking the obtained MOF TiO 2 20mg of NiO photocatalyst, 6mL of sacrificial agent methanol and 24mL of deionized water are added into a sealed glass system, the reaction is carried out after vacuum pumping is carried out for 30min, and the hydrogen generated immediately is detected.
Example 6
Preparation of Ti-ATA: 15.8mmol of 2-amino terephthalic acid is dissolved in 40mL of mixed solvent of N, N-dimethylformamide and 10mL of methanol, 9.7mmol of isopropyl titanate is added, and the mixture is stirred for 5min at room temperature and then transferred into a 100mL reaction kettle; heating the reaction kettle in a 110 ℃ oven for 72 hours, cooling to room temperature, filtering a reaction product, respectively washing the reaction product with N, N-dimethylformamide, methanol and absolute ethyl alcohol for 3 times, and then airing the reaction product in room temperature air to finally obtain yellow powder which is Ti-ATA;
preparation of Ti-ATA-Ni: dissolving 0.06mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, filtering, washing the surface of the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying in a 60 ℃ oven, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with initial Ni molar ratio of 60%;
preparation of MOF TiO 2 NiO: placing Ti-ATA-60% Ni solid powder into a ceramic crucible, calcining in a muffle furnace at 700 ℃ for 2h, and cooling at room temperature to obtain calcined MOF TiO at 700 DEG C 2 -NiO catalyst sample.
Taking the obtained MOF TiO 2 NiO photocatalyst 20mg, sacrificingAdding 6mL of methanol and 24mL of deionized water into a sealed glass system, vacuumizing for 30min, reacting, and detecting hydrogen generated immediately.
Comparative example 1
Preparation of sol-gel TiO 2 NiO: adding 10mmol of isopropyl titanate into a mixed solvent of 50mL of absolute ethyl alcohol, 5mL of glacial acetic acid and 10mL of deionized water, stirring vigorously at room temperature for 10min, adding 6mmol of nickel nitrate, heating in a water bath at 40 ℃ for 2h, and drying the obtained gel product at 80 ℃ for 24h; grinding the obtained solid into powder, and calcining in a muffle furnace at 600 ℃ for 2h to obtain sol-gel TiO 2 -NiO catalyst sample.
Taking the obtained sol-gel TiO 2 20mg of NiO photocatalyst, 6mL of sacrificial agent methanol and 24mL of deionized water are added into a sealed glass system, the reaction is carried out after vacuum pumping is carried out for 30min, and the hydrogen generated immediately is detected.
FIG. 3 shows MOF TiO products of different calcination temperatures in examples 1 to 6 according to the invention 2 Time-yield graph of hydrogen production by catalytic pyrolysis of NiO under UV-visible total light, as can be seen, the optimum calcination temperature is 600℃and the MOF TiO prepared in example 4 2 NiO. FIG. 4 shows MOF TiO prepared in example 4 of the present invention 2 Ni2p XPS spectrum of NiO, analysis shows that the valence of Ni is +2, namely NiO is loaded on TiO after calcination 2 Is a kind of medium.
FIG. 5 shows MOF TiO as prepared in example 4 of the present invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 XRD patterns of NiO, both of which are anatase TiO, as evident from the figure analysis 2 Except for sol-gel TiO 2 XRD of NiO gives a small NiO diffraction peak, while MOF TiO 2 The fact that NiO has no obvious NiO diffraction peak indicates that the NiO loading amount is smaller and the dispersibility is higher in the embodiment, so that the effect of the catalyst promoter is exerted, and the hydrogen production efficiency of the material is improved.
FIG. 6 shows MOF TiO as prepared in example 4 of the present invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 Time-yield profile of NiO catalytic cracking of aqueous hydrogen under uv-vis plenoptic. As can be seen from the figure, MOF TiO prepared in example 4 2 NiO was used in combination with sol-gel TiO prepared in comparative example 1 2 The hydrogen production rates of NiO are 1396. Mu. Mol.h -1 ·g -1 And 127.4. Mu. Mol.h -1 ·g -1 I.e. TiO as obtained by MOF process 2 The hydrogen production efficiency of NiO is TiO obtained by the traditional sol-gel method 2 Nearly 11 times of NiO. FIG. 7 shows MOF TiO as prepared in example 4 of the present invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 FT-IR diagram of NiO, from which MOF TiO can be seen 2 The NiO surface is at 3447cm -1 And 1645cm -1 The characteristic peak ratio of adsorbed water and hydroxyl oxygen at the site is sol-gel TiO 2 The peaks in NiO are strong and broadened, which suggests MOF TiO 2 The NiO surface has more adsorbed water and hydroxyl oxygen, which is beneficial to improving the hydrogen production efficiency of the photocatalytic pyrolysis water.
FIG. 8 shows MOF TiO as prepared in example 4 of the present invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 N of NiO 2 Adsorption-desorption graph with specific surface area of 51.064m 2 /g and 4.086m 2 The larger specific surface area is beneficial to creating a large number of active sites, so that the catalytic efficiency is improved; FIG. 9 shows MOF TiO prepared in example 4 of the present invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 PL spectra of NiO excited at 310nm wavelength, from which MOF TiO can be seen 2 PL peak Jiang Yuan of NiO is weaker than sol-gel TiO 2 NiO, description of light-activated MOF TiO 2 The carrier separation rate of NiO is much higher than that of sol-gel TiO 2 NiO, thus having a higher hydrogen production efficiency; FIG. 10 shows MOF TiO as prepared in example 4 of the present invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 TEM images of NiO, both of which are shown to contain TiO 2 (101) Diffraction fringes characteristic of 0.35nm and NiO (111) 0.24nm, but MOF TiO 2 The particles of NiO are obviously smaller, which is beneficial to improving the hydrogen production efficiency.
To sum up, tiO by MOF method 2 The NiO hydrogen-producing promoter in the NiO material has the advantages of small loading amount, high dispersity, good hydrophilicity, small particles, large specific surface area and higher carrier separation efficiency, so that the high-efficiency photolysis water hydrogen production efficiency is realized.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. Photolytic water production hydrogen MOF TiO 2 -a process for the preparation of NiO materials characterized in that: comprising the steps of (a) a step of,
preparation of Ti-ATA: dissolving 2-amino terephthalic acid in 40mL of a mixed solvent of N, N-dimethylformamide and 10mL methanol, adding isopropyl titanate, stirring at room temperature for 5min, and transferring into a reaction kettle; heating the reaction kettle in an oven, cooling to room temperature, filtering and washing the reaction product, and airing in the air at room temperature to obtain yellow powder which is Ti-ATA;
preparation of Ti-ATA-Ni: dissolving nickel nitrate in 100mL deionized water, adding 100mg of Ti-ATA, stirring at room temperature for 24h, filtering, fully washing the surface of the precipitate, drying in an oven, and drying for a period of time to obtain a Ti-ATA-Ni photocatalyst sample;
preparation of MOF TiO 2 NiO: placing Ti-ATA-Ni solid powder in a ceramic crucible, calcining in a muffle furnace for a period of time, and cooling at room temperature to obtain MOF TiO 2 -NiO photocatalyst sample;
the preparation method of Ti-ATA comprises the steps of adding 10-20 mmol of 2-amino terephthalic acid and 6-15 mmol of isopropyl titanate;
the addition amount of the nickel nitrate is 0.02 mmol~0.1 mmol;
the temperature of the reaction kettle in an oven for heating is 110 ℃ and the time is 72 h;
said preparation of MOF TiO 2 -NiO, wherein the calcination temperature is 450-700 ℃ and the calcination time is 2h.
2. A photolytic water production hydrogen MOF TiO as defined in claim 1 2 -a process for the preparation of NiO materials characterized in that: the reactionThe kettle is a 100mL polytetrafluoroethylene reaction kettle.
3. A photolytic water production hydrogen MOF TiO as defined in claim 1 2 -a process for the preparation of NiO materials characterized in that: in the preparation of Ti-ATA, the washing is performed 3 times with N, N-dimethylformamide, methanol and absolute ethanol, respectively.
4. A photolytic water production hydrogen MOF TiO as defined in claim 1 2 -a process for the preparation of NiO materials characterized in that: when Ti-ATA-Ni is prepared, the washing is carried out for 3 times by deionized water and absolute ethyl alcohol respectively.
5. Photolytic hydroaquatic MOF TiO prepared by the method of any one of claims 1-4 2 -NiO material.
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