CN114950439A - Efficient water photolysis hydrogen production MOF TiO 2 -NiO material and preparation method and application thereof - Google Patents

Efficient water photolysis hydrogen production MOF TiO 2 -NiO material and preparation method and application thereof Download PDF

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CN114950439A
CN114950439A CN202210529921.1A CN202210529921A CN114950439A CN 114950439 A CN114950439 A CN 114950439A CN 202210529921 A CN202210529921 A CN 202210529921A CN 114950439 A CN114950439 A CN 114950439A
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CN114950439B (en
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安阳
姜为易
王玲玲
吕新玲
庞欢
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Yangzhou University
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Abstract

The invention discloses an MOF TiO with high efficiency for photolysis water to produce hydrogen 2 -NiO material and preparation method and application thereof. The nickel compound is widely used as a hydrogen-decomposing auxiliary catalyst for water production, the characteristic that metal nickel ions are easy to coordinate with amino groups contained in organic ligands of metal organic framework materials is utilized, the characteristic that MOFs structure-function is adjustable is utilized, titanium-based MOF Ti-ATA is selected as a precursor material, and high-dispersion Ni-loaded is adopted 2+ Then the catalyst promoter NiO is calcined to obtain the catalyst promoter NiO with high dispersion degree, small material particle size, large specific surface area, high surface hydrophilicity and high efficiencyMOF TiO for photolyzing water to produce hydrogen 2 -a NiO material. The preparation method is simple, the sources of reaction raw materials are wide, the experimental steps are easy to operate, and the method has universality and potential design and research values and can be used for batch production.

Description

Efficient water photolysis hydrogen production MOF TiO 2 -NiO materialMaterial, preparation method and application thereof
Technical Field
The invention belongs to the technical field of photocatalysis, particularly belongs to the technical field of photocatalytic decomposition of hydrogen produced from water, and relates to an MOF TiO for producing hydrogen by efficiently photolyzing water 2 -NiO material and preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The photocatalysis technology has attracted wide attention 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. In recent years, with the increasing problem of energy shortage, hydrogen production by photocatalytic water splitting has attracted more and more attention. The cocatalyst can reduce overpotential of the photocatalytic reaction and promote separation of carriers in the reaction process, so that the cocatalyst is widely used in the field of photolysis of water, and the cocatalyst with high dispersed load can greatly improve the catalysis efficiency.
Titanium dioxide (TiO) 2 ) The photocatalyst is an efficient photocatalyst, has the performance of water splitting, and the direction of attention of the researchers is always how to improve the efficiency of hydrogen production by water photolysis. The nickel-based compound is used as a promoter to greatly improve the hydrogen production activity of the photocatalyst, nickel oxide (NiO) can be used as the hydrogen production promoter, and how to highly disperse the supported NiO is the key to improve 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 and inorganic components of the MOFs are also beneficial to loading of the metal ions with high dispersibility.
Disclosure of Invention
The invention utilizes 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 is adjustable, selects titanium-based MOF Ti-ATA as a precursor material, and loads Ni with high dispersion 2+ Then calcining to obtainThe MOF TiO with high dispersion degree of the catalyst promoter NiO, small material particle size, large specific surface area and high surface hydrophilicity and further capable of efficiently photolyzing water to produce hydrogen 2 -a NiO material.
The present invention has been made keeping in mind the above problems and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a high-efficiency hydrogen MOF (metal organic framework) TiO prepared by photolysis water 2 -NiO material and preparation method and application thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
efficient water photolysis hydrogen production MOF TiO 2 A method for the preparation of a NiO material comprising,
preparing Ti-ATA: dissolving 2-amino terephthalic acid in a mixed solvent of 40mL 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 the reaction product, washing, and airing in air at room temperature to obtain yellow powder, namely Ti-ATA;
preparing Ti-ATA-Ni: dissolving nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature for 24h, fully washing the surface of the precipitate after suction filtration, placing the precipitate in a drying oven for drying, and drying for a period of time to obtain a Ti-ATA-Ni photocatalyst sample;
preparation of MOF TiO 2 -NiO: putting Ti-ATA-Ni solid powder into a ceramic crucible, putting the ceramic crucible into a muffle furnace to calcine for a period of time, and cooling at room temperature to obtain MOF TiO 2 -NiO photocatalyst samples.
Further, the Ti-ATA is prepared, wherein the addition amount of the 2-amino terephthalic acid is 10 mmol-20 mmol, and the addition amount of the isopropyl titanate is 6 mmol-15 mmol.
Further, the reaction kettle is a 100mL polytetrafluoroethylene reaction kettle.
Further, the reaction kettle is placed into an oven to be heated at the temperature of 110 ℃ for 72 hours.
Further, when preparing Ti-ATA, the washing is 3 times of washing with N, N-dimethylformamide, methanol and absolute ethyl alcohol respectively.
Further, the addition amount of the nickel nitrate is 0.02mmol to 0.1 mmol.
Further, when preparing Ti-ATA-Ni, the washing is 3 times of washing with deionized water and absolute ethyl alcohol respectively.
Further, the preparation of MOF TiO 2 NiO, wherein the calcining temperature is 450-700 ℃, and the calcining time is 2 h.
High-efficiency hydrogen MOF TiO prepared by the method through photolysis water 2 -a NiO material.
The MOF TiO 2 The application of the NiO material in the aspect of hydrogen production by photolysis of water has the hydrogen production rate of 1396 mu mol.h under full light -1 ·g -1 。
The invention has the beneficial effects that:
(1) the invention utilizes-NH on organic ligand in Ti-ATA 2 And Ni 2+ Complexing to realize high dispersion of the nickel nitrate. The compound containing Ni2+ is a high-efficiency hydrogen production promoter, and has high catalytic efficiency; is a transition metal, and is easy to complex with amino groups and other groups; low cost, rich storage, no toxicity and easy obtaining.
(2) The method is different from the traditional sol-gel method for preparing TiO 2 According to the characteristics of adjustable structure and function, nickel ions are firstly complexed with amino groups to form bonds by utilizing the amino groups contained in ligands of the MOF material Ti-ATA to obtain Ti-ATA-Ni with highly dispersed or even monodisperse nickel, and the MOF TiO2-NiO photocatalytic material obtained after calcination has larger specific surface area, smaller particles and higher dispersion degree of the supported NiO hydrogen production promoter.
(3) The photocatalytic material prepared by the method shows good photocatalytic activity, and the hydrogen production rate reaches 1396 mu mol.h under full light irradiation -1 ·g -1 。
(4) The method for preparing the photocatalytic material of the invention has the advantages ofApplicability to not only Ni 2+ The same applies to other series of transition metal ions; not only for Ti-ATA, but also for other compounds containing-NH 2 Organic ligand, MOFs and COFs materials.
(5) The preparation method of the photocatalytic material has controllable conditions and results, and simple synthesis method and experimental steps, has great guiding significance in practical application, and has great industrial value.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive labor. Wherein:
FIG. 1 is an XRD pattern of the products Ti-ATA and Ti-ATA-Ni of example 1 of the present invention.
FIG. 2 is a graph of time-yield of the product Ti-ATA-Ni of different initial molar percentages of Ni in example 1 of the present invention produced by catalytically cracking water under full UV-visible light.
FIG. 3 shows the MOF TiO products of examples 1 to 6 of the present invention at different calcination temperatures 2 A time-yield curve diagram of catalytic cracking of water to produce hydrogen by NiO under ultraviolet-visible full light.
FIG. 4 is a MOF TiO prepared according to example 4 of the invention 2 Ni2p XPS spectrum of NiO.
FIG. 5 is a MOF TiO prepared according to example 4 of the invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 XRD pattern of NiO.
FIG. 6 is a MOF TiO prepared according to example 4 of the invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 A time-yield curve diagram of catalytic cracking of water to produce hydrogen by NiO under ultraviolet-visible full light.
FIG. 7 is a MOF TiO prepared according to example 4 of the invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 FT-IR plot of-NiO.
FIG. 8 is a MOF TiO prepared according to example 4 of the invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 N of-NiO 2 Adsorption-desorption curve chart.
FIG. 9 is a MOF TiO prepared according to example 4 of the invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 PL spectrum of NiO at 310nm wavelength excitation.
FIG. 10 is a MOF TiO prepared according to example 4 of the invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 TEM image of NiO.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
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 than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, the references herein to "one embodiment" or "an embodiment" refer to a particular feature, structure, or characteristic that may be included in at least one implementation of the present 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.
The raw material reagents used in the invention: titanium isopropyl ester (Ti (OiPr) 4 ) 2-amino terephthalic acid (H) 2 ATA), N, N-dimethylformamide, methanol, absolute ethanol, nickel nitrate hexahydrate (Ni (NO) 3 ) 2 ·6H 2 O), deionized water. All drugs were of analytical grade (A.R.) and were not further purified.
The glass system used in the present invention is a closed quartz photolytic water reactor (perfect light) with gas inside plus light.
The method for detecting the content of the generated hydrogen comprises the following steps: ar was used as a carrier gas, and the measurement was carried out by a gas chromatograph (Shiweipx GC-7806).
The present invention will be further described with reference to the following examples.
Example 1
Preparing Ti-ATA: dissolving 15.8mmol of 2-amino terephthalic acid in a mixed solvent of 40mL of N, N-dimethylformamide and 10mL of methanol, adding 9.7mmol of isopropyl titanate, stirring at room temperature for 5min, and transferring into a 100mL reaction kettle; heating the reaction kettle in a 110 ℃ oven for 72h, cooling to room temperature, carrying out suction filtration on a reaction product, washing with N, N-dimethylformamide, methanol and absolute ethyl alcohol for 3 times respectively, and then airing in air at room temperature to finally obtain yellow powder, namely Ti-ATA;
preparing Ti-ATA-Ni: dissolving 0.02mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, carrying out suction filtration, respectively washing the surface of the precipitate for 3 times by using the deionized water and absolute ethyl alcohol, drying in a drying oven at 60 ℃, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 20%;
preparing Ti-ATA-Ni: dissolving 0.05mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, carrying out suction filtration, respectively and fully washing the surface of the precipitate for 3 times by using the deionized water and absolute ethyl alcohol, drying in a drying oven at 60 ℃, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 50%;
preparing Ti-ATA-Ni: dissolving 0.055mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, carrying out suction filtration, respectively and fully washing the surface of the precipitate for 3 times by using the deionized water and absolute ethyl alcohol, drying in a drying oven at 60 ℃, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 55%;
preparing Ti-ATA-Ni: dissolving 0.06mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, carrying out suction filtration, respectively and fully washing the surface of the precipitate for 3 times by using the deionized water and absolute ethyl alcohol, drying in a drying oven at 60 ℃, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 60%;
preparing Ti-ATA-Ni: dissolving 0.065mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, performing suction filtration, respectively and fully washing the surface of the precipitate for 3 times by using the deionized water and absolute ethyl alcohol, drying in a drying oven at 60 ℃, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 65%;
preparing Ti-ATA-Ni: dissolving 0.07mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, carrying out suction filtration, respectively and fully washing the surface of the precipitate for 3 times by using the deionized water and absolute ethyl alcohol, drying in a drying oven at 60 ℃, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 70%;
preparing Ti-ATA-Ni: dissolving 0.08mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, performing suction filtration, respectively and fully washing the surface of the precipitate for 3 times by using deionized water and absolute ethyl alcohol, drying in a drying oven at 60 ℃, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 80%;
preparing Ti-ATA-Ni: dissolving 0.09mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, carrying out suction filtration, respectively and fully washing the surface of the precipitate for 3 times by using deionized water and absolute ethyl alcohol, drying in a drying oven at 60 ℃, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 90%;
preparing Ti-ATA-Ni: dissolving 0.1mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, carrying out suction filtration, respectively and fully washing the surface of the precipitate for 3 times by using the deionized water and absolute ethyl alcohol, drying in a drying oven at 60 ℃, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 100%;
and adding 20mg of each obtained Ti-ATA-Ni photocatalyst, 6mL of sacrificial agent methanol and 24mL of deionized water into a sealed glass system, vacuumizing for 30min, reacting, and detecting the instantly generated hydrogen.
FIG. 1 is an XRD diagram of the products Ti-ATA and Ti-ATA-Ni, and it can be seen that the position of the diffraction peak of the sample is not changed after Ni is added, which indicates that Ti-ATA-Ni maintains the framework structure of the original Ti-ATA MOF. Fig. 2 is a time-yield curve diagram of the product Ti-ATA-Ni with different initial molar percentages of Ni catalytically cracked with water under full uv-visible light, and it can be seen by comparison that the initial molar ratio of the optimal performance Ni of Ti-ATA-Ni is 60%, so the optimal Ti-ATA-60% Ni sample is selected for calcination in this and the following examples.
Preparation of MOF TiO 2 -NiO: placing Ti-ATA-60% Ni solid powder in a ceramic crucible, placing the ceramic crucible in a muffle furnace at 450 ℃ for calcining for 2h, and cooling at room temperature to obtain MOF TiO calcined at 450 DEG C 2 -NiO catalyst sample.
Taking the obtained MOF TiO 2 And adding 20mg of NiO photocatalyst, 6mL of sacrificial agent methanol and 24mL of deionized water into a sealed glass system, vacuumizing for 30min, reacting, and detecting the immediately generated hydrogen.
Example 2
Preparing Ti-ATA: dissolving 15.8mmol of 2-amino terephthalic acid in a mixed solvent of 40mL of N, N-dimethylformamide and 10mL of methanol, adding 9.7mmol of isopropyl titanate, stirring at room temperature for 5min, and transferring into a 100mL reaction kettle; heating the reaction kettle in a 110 ℃ oven for 72h, cooling to room temperature, carrying out suction filtration on a reaction product, washing with N, N-dimethylformamide, methanol and absolute ethyl alcohol for 3 times respectively, and then airing in air at room temperature to finally obtain yellow powder, namely Ti-ATA;
preparing Ti-ATA-Ni: dissolving 0.06mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, carrying out suction filtration, respectively and fully washing the surface of the precipitate for 3 times by using the deionized water and absolute ethyl alcohol, drying in a drying oven at 60 ℃, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 60%;
preparation of MOF TiO 2 -NiO: placing Ti-ATA-60% Ni solid powder in a ceramic crucible, placing the ceramic crucible in a muffle furnace at 500 ℃ for calcining for 2h, and cooling at room temperature to obtain MOF TiO calcined at 500 DEG C 2 -NiO catalyst sample.
Taking the obtained MOF TiO 2 Adding 20mg of NiO photocatalyst, 6mL of sacrificial agent methanol and 24mL of deionized water into a sealed glass system, vacuumizing for 30min, and then carrying outReacting and detecting the instantly generated hydrogen.
Example 3
Preparing Ti-ATA: dissolving 15.8mmol of 2-amino terephthalic acid in a mixed solvent of 40mL of N, N-dimethylformamide and 10mL of methanol, adding 9.7mmol of isopropyl titanate, stirring at room temperature for 5min, and transferring into a 100mL reaction kettle; heating the reaction kettle in a 110 ℃ oven for 72h, cooling to room temperature, carrying out suction filtration on a reaction product, washing with N, N-dimethylformamide, methanol and absolute ethyl alcohol for 3 times respectively, and then airing in air at room temperature to finally obtain yellow powder, namely Ti-ATA;
preparing Ti-ATA-Ni: dissolving 0.06mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, carrying out suction filtration, respectively and fully washing the surface of the precipitate for 3 times by using the deionized water and absolute ethyl alcohol, drying in a drying oven at 60 ℃, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 60%;
preparation of MOF TiO 2 -NiO: placing Ti-ATA-60% Ni solid powder in a ceramic crucible, placing the ceramic crucible in a muffle furnace at 550 ℃ for calcining for 2h, and cooling at room temperature to obtain MOF TiO calcined at 550 DEG C 2 -NiO catalyst sample.
Taking the obtained MOF TiO 2 And adding 20mg of NiO photocatalyst, 6mL of sacrificial agent methanol and 24mL of deionized water into a sealed glass system, vacuumizing for 30min, reacting, and detecting the immediately generated hydrogen.
Example 4
Preparing Ti-ATA: dissolving 15.8mmol of 2-amino terephthalic acid in a mixed solvent of 40mL of N, N-dimethylformamide and 10mL of methanol, adding 9.7mmol of isopropyl titanate, stirring at room temperature for 5min, and transferring into a 100mL reaction kettle; heating the reaction kettle in a 110 ℃ oven for 72h, cooling to room temperature, carrying out suction filtration on a reaction product, washing with N, N-dimethylformamide, methanol and absolute ethyl alcohol for 3 times respectively, and then airing in air at room temperature to finally obtain yellow powder, namely Ti-ATA;
preparing Ti-ATA-Ni: dissolving 0.06mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, carrying out suction filtration, respectively and fully washing the surface of the precipitate for 3 times by using the deionized water and absolute ethyl alcohol, drying in a drying oven at 60 ℃, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 60%;
preparation of MOF TiO 2 -NiO: putting Ti-ATA-60% Ni solid powder into a ceramic crucible, putting the ceramic crucible into a muffle furnace at 600 ℃ for calcining for 2h, and cooling at room temperature to obtain 600 ℃ calcined MOF TiO 2 -NiO catalyst sample.
Taking the obtained MOF TiO 2 And adding 20mg of NiO photocatalyst, 6mL of sacrificial agent methanol and 24mL of deionized water into a sealed glass system, vacuumizing for 30min, reacting, and detecting the immediately generated hydrogen.
Example 5
Preparing Ti-ATA: dissolving 15.8mmol of 2-amino terephthalic acid in a mixed solvent of 40mL of N, N-dimethylformamide and 10mL of methanol, adding 9.7mmol of isopropyl titanate, stirring at room temperature for 5min, and transferring into a 100mL reaction kettle; heating the reaction kettle in a 110 ℃ oven for 72h, cooling to room temperature, carrying out suction filtration on a reaction product, washing with N, N-dimethylformamide, methanol and absolute ethyl alcohol for 3 times respectively, and then airing in air at room temperature to finally obtain yellow powder, namely Ti-ATA;
preparing Ti-ATA-Ni: dissolving 0.06mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, carrying out suction filtration, respectively and fully washing the surface of the precipitate for 3 times by using the deionized water and absolute ethyl alcohol, drying in a drying oven at 60 ℃, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 60%;
preparation of MOF TiO 2 -NiO: putting Ti-ATA-60% Ni solid powder into a ceramic crucible, putting the ceramic crucible into a muffle furnace at 650 ℃ for calcining for 2h, and cooling at room temperature to obtain calcined MOF TiO at 650 DEG C 2 -NiO catalyst sample.
Taking the obtained MOF TiO 2 And adding 20mg of NiO photocatalyst, 6mL of sacrificial agent methanol and 24mL of deionized water into a sealed glass system, vacuumizing for 30min, reacting, and detecting the immediately generated hydrogen.
Example 6
Preparing Ti-ATA: dissolving 15.8mmol of 2-amino terephthalic acid in a mixed solvent of 40mL of N, N-dimethylformamide and 10mL of methanol, adding 9.7mmol of isopropyl titanate, stirring at room temperature for 5min, and transferring into a 100mL reaction kettle; heating the reaction kettle in a 110 ℃ oven for 72h, cooling to room temperature, carrying out suction filtration on a reaction product, washing with N, N-dimethylformamide, methanol and absolute ethyl alcohol for 3 times respectively, and then airing in air at room temperature to finally obtain yellow powder, namely Ti-ATA;
preparing Ti-ATA-Ni: dissolving 0.06mmol of nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature, carrying out suction filtration, respectively and fully washing the surface of the precipitate for 3 times by using the deionized water and absolute ethyl alcohol, drying in a drying oven at 60 ℃, and drying for 12 hours to obtain a Ti-ATA-Ni photocatalyst sample with the initial molar ratio of Ni of 60%;
preparation of MOF TiO 2 -NiO: placing Ti-ATA-60% Ni solid powder in a ceramic crucible, placing the ceramic crucible in a muffle furnace at 700 ℃ for calcining for 2h, and cooling at room temperature to obtain 700 ℃ calcined MOF TiO 2 -NiO catalyst sample.
Taking the obtained MOF TiO 2 And adding 20mg of NiO photocatalyst, 6mL of sacrificial agent methanol and 24mL of deionized water into a sealed glass system, vacuumizing for 30min, reacting, and detecting the immediately generated hydrogen.
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, violently stirring for 10min at room temperature, adding 6mmol of nickel nitrate, heating in a water bath at 40 ℃ for 2h, and drying the obtained gel product for 24h at 80 ℃; grinding the obtained solid into powder, and calcining the powder in a muffle furnace at 600 ℃ for 2h to obtain sol-gel TiO 2 -NiO catalyst sample.
Taking the obtained sol-gel TiO 2 And adding 20mg of NiO photocatalyst, 6mL of sacrificial agent methanol and 24mL of deionized water into a sealed glass system, vacuumizing for 30min, reacting, and detecting the immediately generated hydrogen.
FIG. 3 shows MOF TiO products of examples 1 to 6 of the present invention at different calcination temperatures 2 Time-yield of catalytic cracking of water to produce hydrogen with NiO under full UV-visible lightThe graph shows that the optimum performance calcination temperature is 600 ℃, i.e., MOF TiO prepared in example 4 2 -NiO. FIG. 4 is a MOF TiO prepared according to example 4 of the invention 2 Analysis of Ni2p XPS spectrum of NiO revealed that the valence of Ni was +2, that is, NiO was supported on TiO in the state of NiO after calcination 2 In (1).
FIG. 5 is a MOF TiO prepared according to example 4 of the invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 XRD pattern of NiO, both of which are anatase TiO, as analyzed 2 Except that sol-gel TiO 2 The XRD of NiO has one more small NiO diffraction peak, while MOF TiO 2 NiO has no obvious NiO diffraction peak, which shows that the NiO in the embodiment has smaller load and higher dispersity, and is beneficial to playing the role of the promoter so as to improve the hydrogen production efficiency of the material.
FIG. 6 is a MOF TiO prepared according to example 4 of the invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 The time-output curve graph of the NiO for catalytically cracking water to produce hydrogen under the ultraviolet-visible full light is shown. As can be seen from the figure, the MOF TiO prepared in example 4 2 NiO-gel TiO prepared in comparative example 1 2 The hydrogen production rates of-NiO are 1396 mu mol · h respectively -1 ·g -1 And 127.4. mu. mol. h -1 ·g -1 I.e. TiO from MOF processes 2 The hydrogen production efficiency of the-NiO is TiO obtained by the traditional sol-gel method 2 Nearly 11 times that of NiO. FIG. 7 is a MOF TiO prepared according to example 4 of the invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 FT-IR diagram of-NiO, from which MOF TiO 2 The NiO surface is located at 3447cm -1 And 1645cm -1 The characteristic peak ratio of adsorbed water and hydroxyl oxygen of sol-gel TiO 2 The peak in-NiO is strong and broadened, which indicates MOF TiO 2 The NiO surface absorbs more water and hydroxyl oxygen, and the hydrogen production efficiency of photocatalytic cracking water is improved.
FIG. 8 is a MOF TiO prepared according to example 4 of the invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 N of-NiO 2 The specific surface areas of the adsorption graph and the desorption graph are 51.064m respectively 2 G and 4.086m 2 The larger specific surface area is beneficial to wound healingA large number of active sites are created, and the catalytic efficiency is further improved; FIG. 9 is a MOF TiO prepared according to example 4 of the invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 PL spectrum of 310nm wavelength excitation of NiO, from which MOF TiO 2 PL peak intensity of-NiO is far weaker than that of sol-gel TiO 2 NiO, indicating photo-excited MOF TiO 2 The carrier separation speed of the-NiO is much higher than that of sol-gel TiO 2 -NiO, thereby having a higher hydrogen production efficiency; FIG. 10 is a MOF TiO prepared according to example 4 of the invention 2 NiO and sol-gel TiO prepared in comparative example 1 2 TEM image of-NiO, showing that both contain TiO 2 (101)0.35nm and NiO (111)0.24nm characteristic diffraction fringes, but MOF TiO 2 The particles of NiO are obviously smaller, which is beneficial to improving the hydrogen production efficiency.
To sum up, the MOF method yields TiO 2 The NiO hydrogen production promoter in the NiO material has the advantages of low load, high dispersity, good hydrophilicity, small particles, large specific surface area and high carrier separation efficiency, so that the high-efficiency photolysis hydrogen production efficiency is realized.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. Efficient water photolysis hydrogen production MOF TiO 2 -a method for the preparation of a NiO material, characterized in that: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
preparing Ti-ATA: dissolving 2-amino terephthalic acid in a mixed solvent of 40mL 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 the reaction product, washing, and airing in air at room temperature to obtain yellow powder, namely Ti-ATA;
preparing Ti-ATA-Ni: dissolving nickel nitrate in 100mL of deionized water, adding 100mg of Ti-ATA, stirring at room temperature for 24h, fully washing the surface of the precipitate after suction filtration, placing the precipitate in a drying oven for drying, and drying for a period of time to obtain a Ti-ATA-Ni photocatalyst sample;
preparation of MOF TiO 2 -NiO: putting Ti-ATA-Ni solid powder into a ceramic crucible, putting the ceramic crucible into a muffle furnace to calcine for a period of time, and cooling at room temperature to obtain MOF TiO 2 -NiO photocatalyst samples.
2. The MOF TiO with high efficiency of photolysis-hydrolysis hydrogen production according to claim 1 2 -a method for the preparation of a NiO material, characterized in that: the Ti-ATA is prepared, wherein the addition amount of the 2-amino terephthalic acid is 10 mmol-20 mmol, and the addition amount of the isopropyl titanate is 6 mmol-15 mmol.
3. The MOF TiO with high efficiency of photolysis-hydrolysis hydrogen production according to claim 1 2 -a method for the preparation of a NiO material, characterized in that: the reaction kettle is a 100mL polytetrafluoroethylene reaction kettle.
4. The MOF TiO with high efficiency of photolysis-hydrolysis hydrogen production according to claim 1 2 -a method for the preparation of a NiO material, characterized in that: the reaction kettle is placed into an oven to be heated at the temperature of 110 ℃ for 72 hours.
5. The MOF TiO with high efficiency of photolysis-hydrolysis hydrogen production according to claim 1 2 -a method for the preparation of a NiO material, characterized in that: when Ti-ATA is prepared, the washing is 3 times of washing by N, N-dimethylformamide, methanol and absolute ethyl alcohol respectively.
6. The MOF/TiO with high efficiency of photolysis and hydrolysis for hydrogen production as claimed in claim 1 2 -a method for the preparation of a NiO material, characterized in that: the addition amount of the nickel nitrate is 0.02 mmol-0.1 mmol.
7. The MOF/TiO with high efficiency of photolysis and hydrolysis for hydrogen production as claimed in claim 1 2 -a method for the preparation of a NiO material, characterized in that: when preparing Ti-ATA-Ni, the washing is to use deionized water and absolute ethyl alcoholWashing 3 times.
8. The MOF TiO with high efficiency of photolysis-hydrolysis hydrogen production according to claim 1 2 -a method for the preparation of a NiO material, characterized in that: the preparation of MOF TiO 2 NiO, wherein the calcining temperature is 450-700 ℃, and the calcining time is 2 h.
9. The high-efficiency photolytic hydrohydrogenesis MOF TiO prepared by the method of any one of claims 1 to 8 2 -a NiO material.
10. The MOF TiO of claim 9 2 The application of the NiO material in the aspect of hydrogen production by photolysis of water is characterized in that the hydrogen production rate under full light irradiation reaches 1396 mu mol.h -1 ·g -1 。
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