CN111910431B - Metal iridium-based composite material, preparation method thereof and photocatalytic hydrolysis method - Google Patents

Metal iridium-based composite material, preparation method thereof and photocatalytic hydrolysis method Download PDF

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CN111910431B
CN111910431B CN202010801539.2A CN202010801539A CN111910431B CN 111910431 B CN111910431 B CN 111910431B CN 202010801539 A CN202010801539 A CN 202010801539A CN 111910431 B CN111910431 B CN 111910431B
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metal iridium
maleic anhydride
composite material
iridium complex
based composite
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CN111910431A (en
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张依帆
王月
柳美华
魏巍
郑春柏
邓鹏飏
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Changchun Institute of Applied Chemistry of CAS
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    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
    • D06M14/28—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • 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
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Abstract

The invention provides a metal iridium-based composite material, a preparation method thereof and a photocatalytic hydrolysis method. The invention provides a metallic iridium-based composite material, which comprises: the metal iridium complex comprises a high-molecular polymer solid-phase substrate material, maleic anhydride molecules grafted to the high-molecular polymer solid-phase substrate material and a metal iridium complex covalently connected with the maleic anhydride molecules; according to the invention, maleic anhydride molecules are grafted on a high molecular polymer fixed substrate material, and then the metal iridium complex shown in the formula (1) is covalently connected with the maleic anhydride molecules to form a specific metal iridium-based composite material, so that the stability of the photosensitizer in the photocatalytic hydrolysis hydrogen production process can be effectively improved, the photocatalyst hydrolysis hydrogen production system has a super-long service life, and the excellent hydrogen production activity is maintained.

Description

Metal iridium-based composite material, preparation method thereof and photocatalytic hydrolysis method
Technical Field
The invention relates to the field of photocatalytic hydrolysis, in particular to a metal iridium-based composite material, a preparation method thereof and a photocatalytic hydrolysis method.
Background
With the development of society and science and technology, energy and environmental protection are two major topics of the current society. The use of fossil fuel in large quantities not only causes energy shortage, but also brings about serious problems of environmental pollution and the like. The development and utilization of clean and renewable novel energy sources are major challenges facing social development.
The hydrogen energy has the advantages of good combustibility, cleanness and the like, and is an ideal candidate for replacing fossil energy. However, at present, the industrial hydrogen acquisition mainly depends on water electrolysis, and the energy consumption is large. The average power of the sun on the earth surface is about 120000TW, which is 10000 times of the current energy consumption rate of human society. More importantly, the solar energy does not need to be transported, is distributed relatively uniformly, is environment-friendly and is an ideal energy source for social development. How to effectively convert solar energy into hydrogen energy is the focus of attention in the field of photoelectric conversion. The photocatalytic water splitting hydrogen production technology utilizes abundant water resources in nature, and is an ideal mode for converting solar energy into hydrogen energy. However, it is relatively difficult to directly decompose water into hydrogen and oxygen, and researchers have added a sacrificial agent into a photocatalytic water decomposition system to separately study the two half reactions of water reduction and water oxidation.
In 2005, the Bernhard group applied the iridium complex as a Photosensitizer (PS) to a photocatalytic hydrolysis hydrogen production system for the first time. Studies have shown that in PS- [ Co (bpy)3]Cl2In the system of TEOA, the hydrogen production of all photosensitizers based on iridium complexes is higher than that of the reference photosensitizer, namely the polypyridyl ruthenium complex. This is because iridium has a larger atomic number than ruthenium, and enhances the splitting energy of the ligand field. Meanwhile, sigma bonds exist between ligands and iridium centers in the iridium complex, and chemical bonds between the ligands and the ruthenium centers in the polypyridyl ruthenium complex are coordination bonds, so that the iridium complex has better stability and is more suitable to be used as a photosensitizer to be applied to a photocatalytic water splitting hydrogen production system.
In 2007, the subject group explores the photocatalytic process in detail by taking a classical ionic metal iridium complex as a photosensitizer, triethanolamine as a sacrificial agent and platinum as a catalyst. They believe that first the photosensitizer absorbs light energy to form an excited state, then the triethanolamine gives off electrons and the iridium photosensitizer in the excited state gains electrons to form a reduced state. The reduced photosensitizer then transfers electrons to the platinum catalyst, the photosensitizer returns to the ground state, and water is reduced to hydrogen gas by the platinum catalyst. In addition, this article was also studied for the process of photosensitizer inactivation. The mass spectrum result shows that the metal iridium complex in the solution is not changed before illumination, and after illumination for a period of time, two new peaks appear in the mass spectrum, which respectively correspond to the molecular weight of the iridium complex after bipyridyl stripping and the molecular weight of the new complex formed by coordination of the iridium complex and the acetonitrile solvent after bipyridyl stripping; this result is a visual demonstration that the photocatalytic system deactivation is due to the shedding of the photosensitizer bipyridine ligand.
Subsequently, the subject group replaced the original bidentate ligand of the photosensitizer with a tridentate ligand. The photocatalysis experiment shows that the service life of the photosensitizer is obviously longer than that of the photosensitizer of the original bidentate ligand. In the Zhongxiong subject group, a series of neutral iridium photosensitizers are reported, original bipyridyl is replaced by phenylpyridine, and the service life of the iridium photosensitizers can be effectively prolonged.
The Park topic group reports a series of metallic iridium photosensitizers containing a triphenyl silicon group. The service life of the photosensitizer can be improved to the maximum extent by the triphenyl silicon group with larger volume, and the photosensitizer containing the triphenyl silicon group has long service life, and the best result is 144 hours. How to further improve the service life of the photosensitizer is still one of the main development directions in the field.
Disclosure of Invention
In view of the above, the present invention provides a metal iridium-based composite material, a preparation method thereof, and a photocatalytic hydrolysis method. The metal iridium-based composite material provided by the invention can effectively prolong the service life of the photosensitizer.
The invention provides a metal iridium-based composite material, which comprises:
the metal iridium complex comprises a high-molecular polymer solid-phase substrate material, maleic anhydride molecules grafted to the high-molecular polymer solid-phase substrate material and a metal iridium complex covalently connected with the maleic anhydride molecules;
the metal iridium complex has a structure shown in a formula (1):
Figure BDA0002627566810000021
wherein the content of the first and second substances,
Figure BDA0002627566810000031
one selected from the group consisting of the structures shown in formulas a to e:
Figure BDA0002627566810000032
preferably, the high molecular polymer in the high molecular polymer solid phase substrate material is selected from one or more of ultrahigh molecular polyethylene, polypropylene, polyethylene terephthalate, polytetrafluoroethylene and polyimide.
Preferably, the high molecular polymer solid phase substrate material is fiber, non-woven fabric or porous film.
Preferably, the grafting density of the maleic anhydride on the high polymer solid phase substrate material is 15-75 nmol/cm2。
The invention also provides a preparation method of the metal iridium-based composite material in the technical scheme, which comprises the following steps:
a) soaking a high molecular polymer solid phase substrate material in a solution of maleic anhydride, and performing irradiation grafting to obtain a high molecular solid phase substrate material grafted with maleic anhydride;
b) reacting the maleic anhydride grafted polymer solid phase substrate material with the metal iridium complex shown in the formula (1) in a solvent to obtain the metal iridium-based composite material covalently connected with the metal iridium complex shown in the formula (1).
Preferably, in step a):
the mass fraction of the maleic anhydride solution is 10-70%;
the radiation source of the irradiation grafting is a cobalt 60 source or an electron accelerator;
the dose of the irradiation grafting is 5-100 kGy, and the dose rate is 0.3-5 kGy/h.
Preferably, the step b) includes:
b1) dissolving a metal iridium complex shown in a formula (1) in a solvent to obtain a metal iridium complex solution;
b2) soaking the maleic anhydride grafted polymer solid phase substrate material in the metal iridium complex solution for reaction to obtain a metal iridium-based composite material covalently connected with the metal iridium complex in the formula (1);
the concentration of the metal iridium complex solution is 0.5-1.5 g/L;
the reaction temperature is 100-120 ℃, and the reaction time is 8-12 h.
Preferably, the step a), after the irradiation grafting, further comprises: cleaning and drying;
in the step b), after the reaction, the method further comprises: and (4) cleaning and drying.
The invention also provides a photocatalytic hydrolysis method, which comprises the following steps:
under the action of a photosensitizer, the photocatalytic system is hydrolyzed to generate hydrogen;
the photocatalytic system comprises a catalyst, a sacrificial agent, and water;
the photosensitizer is the metal iridium-based composite material in the technical scheme.
Preferably, the catalyst comprises potassium chloroplatinite, [ Co (bpy)3]Cl2And [ Rh (dtbbpy)](PF6)2One or more of the above;
the sacrificial agent is triethylamine and/or triethanolamine.
According to the invention, maleic anhydride molecules are grafted on a high molecular polymer fixed substrate material, and then the metal iridium complex shown in the formula (1) is covalently connected with the maleic anhydride molecules to form a specific metal iridium-based composite material, so that the stability of the photosensitizer in the photocatalytic hydrolysis hydrogen production process can be effectively improved, the photocatalyst hydrolysis hydrogen production system has a super-long service life, and the excellent hydrogen production activity is maintained.
Test results show that the metallic iridium-based composite material provided by the invention can continuously produce hydrogen for more than 300 hours in a photocatalytic system, and has an ultra-long service life; and the composite material has excellent hydrogen production activity in an overlong using process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a metallic iridium-based composite material provided by the present invention;
FIG. 2 is a schematic diagram of the structure of maleic anhydride grafted onto a high molecular weight polymer solid substrate material;
FIG. 3 is a schematic structural diagram of a polymeric substrate-maleic anhydride-iridium complex;
FIG. 4 is a schematic view of a reaction process;
FIG. 5 shows the product obtained in example 11H NMR test chart;
FIG. 6 shows the product obtained in example 21H NMR test chart;
FIG. 7 is a XPS and EDS test chart of the product obtained in example 6;
FIG. 8 is a graph showing the photocatalytic hydrolysis hydrogen production effect of the iridium-based composite material obtained in example 6;
FIG. 9 is a graph showing the photocatalytic hydrolysis hydrogen production effect of the iridium-based composite material obtained in example 7;
FIG. 10 is a graph showing the photocatalytic hydrolysis hydrogen production effect of the iridium-based composite material obtained in example 8;
FIG. 11 is a graph showing the photocatalytic hydrolysis hydrogen production effect of the composite material obtained in comparative example 1.
Detailed Description
The invention provides a metal iridium-based composite material, which is characterized by comprising the following components in percentage by weight:
the metal iridium complex comprises a high-molecular polymer solid-phase substrate material, maleic anhydride molecules grafted to the high-molecular polymer solid-phase substrate material and a metal iridium complex covalently connected with the maleic anhydride molecules;
the metal iridium complex has a structure shown in a formula (1):
Figure BDA0002627566810000051
wherein the content of the first and second substances,
Figure BDA0002627566810000052
one selected from the group consisting of the structures shown in formulas a to e:
Figure BDA0002627566810000053
according to the invention, maleic anhydride molecules are grafted on a high molecular polymer fixed substrate material, and then the metal iridium complex shown in the formula (1) is covalently connected with the maleic anhydride molecules to form a specific metal iridium-based composite material, so that the stability of the photosensitizer in the photocatalytic hydrolysis hydrogen production process can be effectively improved, and the photocatalyst hydrolysis hydrogen production system has an ultra-long service life and excellent hydrogen production activity.
In the invention, the structure of the iridium-based composite material is shown in fig. 1, and fig. 1 is a schematic structural diagram of the iridium-based composite material provided by the invention; wherein 1 represents a high molecular polymer solid phase substrate material, and octahedron represents a metal iridium complex shown in a formula (1). In the metal iridium-based composite material, a maleic anhydride molecule is grafted to a high molecular polymer in a high molecular solid phase substrate material, and a metal iridium complex shown in a formula (1) is covalently connected to the maleic anhydride molecule.
In the invention, the high molecular polymer in the high molecular polymer solid phase substrate material is preferably one or more of ultrahigh molecular polyethylene (UHMWPE), polypropylene (PP), polyethylene terephthalate (PET), Polytetrafluoroethylene (PTFE) and Polyimide (PI). The high molecular weight polymer generally refers to a high molecular weight polymer (usually 10 to 10) formed by repeating a simple structural unit through a covalent bond6) The macromolecular compound of (2) is referred to as a polymer in the present invention.
In the invention, the state of the high molecular polymer solid phase substrate material is preferably fiber, non-woven fabric or porous film, namely the composite material provided by the invention is a material with macroscopic size.
In the invention, the grafting density of the maleic anhydride on the high polymer solid phase substrate material is preferably 15-75 nmol/cm2. The structure of maleic anhydride grafted onto high molecular polymer solid phase substrate is shown in fig. 2, fig. 2 is a schematic structural diagram of maleic anhydride grafted onto high molecular polymer solid phase substrate, wherein 1 represents high molecular polymer solid phase substrate. The structure of maleic anhydride grafted on high molecular polymer isThe structures known to the person skilled in the art, such as for the above 5 high molecular polymers, the grafted materials obtained after grafting the maleic anhydride molecules are generally abbreviated to UHMWPE-g-MAH, PP-g-MAH, PET-g-MAH, PTFE-g-MAH, PI-g-MAH. Specifically, high-energy radiation rays are irradiated on the surface of the polymer, which causes the main chain or the branched chain of the polymer to be cut off, the polymer loses H or C, a free radical is formed, the free radical further reacts with a double bond of maleic anhydride (free radical reaction), the maleic anhydride is grafted onto the polymer substrate, the structural schematic diagram is shown in fig. 3, and fig. 3 is a structural schematic diagram of the polymer substrate-maleic anhydride-iridium complex.
In the invention, the metal iridium complex has a structure shown in a formula (1):
Figure BDA0002627566810000061
wherein the content of the first and second substances,
Figure BDA0002627566810000062
one selected from the group consisting of the structures shown in formulas a to e:
Figure BDA0002627566810000071
namely, the metal iridium complex shown in the formula (1) is selected from the following 5 compounds:
Figure BDA0002627566810000072
in the invention, in the metallic iridium-based composite material, the molar ratio of the metallic iridium complex shown in the formula (1) to the maleic anhydride molecule is preferably (0.1-1) to 1.
In the present invention, the iridium complex of the metal represented by the formula (1) can be prepared by the following method:
s1) reacting the dichloro-bridge compound 2 with silver hexafluorophosphate in a methanol medium to form an intermediate 3;
s2) reacting the intermediate 3 with 4,4 '-diamino-2, 2' -bipyridyl in a polar organic solvent in the presence of ammonium hexafluorophosphate to form a metal iridium complex shown in the formula (1);
Figure BDA0002627566810000073
wherein, the dichloro bridge compound 2 is selected from one of formulas 2a to 2 e:
Figure BDA0002627566810000081
with respect to step S1):
the dichloro-bridge compound 2 is a primary ligand selected from the group consisting of ppy dichloro-bridges (i.e., [ Ir (ppy))2(μ-Cl)]2) Tpy dichloro bridge (i.e., [ Ir (tpy))2(μ-Cl)]2) Btp dichloro bridge (i.e., [ Ir (btp))2(μ-Cl)]2)、F2ppy dichloro bridge (i.e., [ Ir (F))2ppy)2(μ-Cl)]2) Or F2bpy dichloro bridge (i.e., [ Ir (F))2bpy)2(μ-Cl)]2) (ii) a Specifically, the compounds are represented by the above formulas 2a to 2e, respectively.
The mol ratio of the dichloro-bridge compound 2 to the silver hexafluorophosphate is preferably 1 to (2-2.5). In some embodiments of the invention, the molar ratio is 1: 2.2.
The methanol both acts as a solvent and participates in the reaction to form intermediates. The dosage ratio of the dichloro-bridge compound 2 to the methanol is preferably (0.8-1) mmol to (70-100) mL.
The reaction temperature is not particularly limited, and may be room temperature, specifically 20 to 25 ℃. The reaction time is preferably 2-3 h, and in some embodiments of the invention, the reaction time is 2 h. The 3 raw materials are subjected to coordination reaction and anion exchange reaction at room temperature, so that an intermediate 3 is formed.
After the reaction, it is preferable to further include: the reaction mixture was filtered to remove the precipitate, and the resulting solution was dried to remove the solvent. Wherein the drying preferably comprises spin drying (i.e. rotary evaporation) and oven drying. The product obtained by drying is the intermediate 3.
With respect to step S2):
the ammonium hexafluorophosphate is added in excess in order to complete the anion exchange of the iridium complex. Specifically, the molar ratio of the intermediate 3 to ammonium hexafluorophosphate is preferably 1: (10-15).
The 4,4 '-diamino-2, 2' -bipyridyl is an auxiliary ligand, and the molar ratio of the intermediate 3 to the 4,4 '-diamino-2, 2' -bipyridyl is preferably 1: 1-1.2; in some embodiments of the invention, the molar ratio is 1: 1.
The above-mentioned various raw materials are reacted in a polar organic solvent, the kind of the polar organic solvent is not particularly limited in the present invention, and the polar organic solvent may be a conventional polar solvent well known to those skilled in the art, and the present invention specifically preferably includes one or more of methanol, dichloromethane, acetonitrile and acetone. In the invention, the dosage ratio of the intermediate 3 to the solvent is preferably (0.5-1) mmol to (40-100) mL.
The reaction temperature is not particularly limited, and may be room temperature, specifically 20 to 25 ℃. The reaction time is preferably 2-3 h, and in some embodiments of the invention, the reaction time is 2 h. The above raw materials undergo a coordination reaction and further anion exchange reaction at room temperature to form a metal iridium complex represented by the formula (1).
After the reaction, it is preferable to further include: the reaction mixture was filtered to remove precipitates, and the resulting solution was dried and subjected to column separation by stir-frying. Wherein the drying is preferably spin drying. The solvent used for stir-frying the sample is preferably one or more of dichloromethane, methanol and acetone. The eluent used for the column chromatography is preferably petroleum ether, ethyl acetate, dichloromethane and acetone; the volume ratio of the four eluents is preferably 1 to (0.5-2) to (0.05-0.5). After separation, the obtained solid product is the metal iridium complex shown in the formula (1).
According to the invention, maleic anhydride molecules are grafted on a high molecular polymer fixed substrate material, and then the metal iridium complex shown in the formula (1) is covalently connected with the maleic anhydride molecules to form a specific metal iridium-based composite material, so that the stability of the photosensitizer in the photocatalytic hydrolysis hydrogen production process can be effectively improved, and the photocatalyst hydrolysis hydrogen production system has a super-long service life.
The invention also provides a preparation method of the metal iridium-based composite material in the technical scheme, which comprises the following steps:
a) soaking a high molecular polymer solid phase substrate material in a solution of maleic anhydride, and performing irradiation grafting to obtain a high molecular solid phase substrate material grafted with maleic anhydride;
b) reacting the maleic anhydride grafted polymer solid phase substrate material with the metal iridium complex shown in the formula (1) in a solvent to obtain the metal iridium-based composite material covalently connected with the metal iridium complex shown in the formula (1).
The types and forms of the high molecular polymer solid phase substrate materials, the grafting condition of maleic anhydride, the structure of the metal iridium complex in the formula (1), and the like are consistent with those in the technical scheme, and are not described in detail herein.
With respect to step a):
the high molecular polymer solid phase substrate material is preferably washed and dried before use.
The solution of the maleic anhydride is formed by dissolving solid maleic anhydride in a solvent. In the present invention, the mass fraction of the solution is preferably 10% to 70%. The kind of the solvent is not particularly limited, and it is sufficient that maleic anhydride can be dissolved, and the present invention preferably includes one or more of tetrahydrofuran, ethanol, ethyl acetate, and propanol.
When the high molecular polymer solid phase substrate material is immersed in the solution of maleic anhydride, the dosage of the solution is not particularly limited, and the high molecular polymer solid phase substrate material can be completely immersed. After immersion, the vessel is preferably sealed and then radiation grafted.
The temperature of the irradiation grafting is not particularly limited, and the irradiation grafting can be carried out at room temperature, and specifically can be 20-25 ℃. The conditions for the radiation grafting are preferably: the radiation source is a cobalt 60 source or an electron accelerator; the irradiation dose is 5-100 kGy; the irradiation dose rate is 0.3-5 kGy/h. After irradiation grafting, a grafting reaction occurs to form a high molecular solid phase substrate material grafted with maleic anhydride, and the structural schematic diagram is shown in fig. 2.
After the radiation grafting, washing and drying are preferably also carried out. The washing is preferably ultrasonic washing. The drying temperature is preferably 50-65 ℃. After the above treatment, a graft material was obtained.
With respect to step b):
the operation steps preferably comprise:
b1) dissolving a metal iridium complex shown in a formula (1) in a solvent to obtain a metal iridium complex solution;
b2) and (2) soaking the maleic anhydride grafted polymer solid phase substrate material in the metal iridium complex solution for reaction to obtain the metal iridium-based composite material covalently connected with the metal iridium complex in the formula (1).
The solvent is preferably one or more of dioxane, tetrahydrofuran and toluene. The mass concentration of the metal iridium complex shown in the formula (1) in a solvent is preferably 0.5-1.5 g/L.
When the impregnation operation is carried out, the using amount of the two materials is not particularly limited, and the metal iridium complex solution can completely immerse the high polymer solid phase substrate material grafted with the maleic anhydride.
The reaction temperature is preferably 100-120 ℃; in some embodiments of the invention, the reaction temperature is 110 ℃. The reaction time is preferably 8-12 h; in some embodiments of the invention, the reaction time is 9 hours. After the reaction, the metallic iridium complex shown in the formula (1) is covalently linked with maleic anhydride to form the metallic iridium-based composite material, wherein the reaction process is shown in fig. 4, and fig. 4 is a schematic diagram of the reaction process.
In the present invention, it is preferable to further perform washing and drying after the above reaction. The washing is preferably ultrasonic washing. The drying is preferably vacuum drying; the drying temperature is preferably 50-65 ℃. And drying to obtain the metal iridium-based composite material.
The invention also provides a photocatalytic hydrolysis method, which comprises the following steps:
under the action of a photosensitizer, the photocatalytic system is hydrolyzed to generate hydrogen;
the photocatalytic system comprises a catalyst, a sacrificial agent, and water;
the photosensitizer is the metal iridium-based composite material in the technical scheme.
The metal iridium-based composite material provided by the invention is used as a photosensitizer applied to a photocatalytic system, so that the service life can be effectively prolonged, and high-efficiency hydrogen production can be maintained for a long time.
The photocatalytic system includes a catalyst, a sacrificial agent, and water, which are conventional constituents of photocatalytic systems.
Wherein:
the catalyst preferably comprises potassium chloroplatinite, [ Co (bpy)3]Cl2And [ Rh (dtbbpy)](PF6)2One or more of them.
The sacrificial agent is preferably triethylamine and/or triethanolamine. The dosage ratio of the catalyst to the sacrificial agent is preferably (1-40) mu mol to (2-20) mL.
The molar ratio of the molar amount of the metal iridium complex in the photosensitizer to the molar amount of the catalyst is preferably 1 to (0.4-10).
The dosage ratio of the catalyst to water is preferably 3 mu mol to (10-30) mL.
The photocatalytic system preferably also comprises an organic solvent. The organic solvent preferably comprises one or more of dimethylformamide (i.e., DMF), tetrahydrofuran (i.e., THF), and acetone. The dosage ratio of the catalyst to the organic solvent is preferably 3 mu mol to (50-70) mL.
Under the action of the photosensitizer and the illumination condition, the photocatalytic system is hydrolyzed to generate hydrogen. The metal iridium-based composite material provided by the invention is used as a photosensitizer applied to a photocatalytic system, can effectively improve the stability of the photosensitizer in the photocatalytic hydrolysis hydrogen production process, and has a super-long service life in the photocatalytic hydrolysis hydrogen production system.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
1.1 preparation
S1, adding ppy dichloro-bridge (0.8975g,0.838mmol) and silver hexafluorophosphate (0.464g,1.84mmol) into 70mL of methanol solvent, stirring at room temperature for 2h, carrying out suction filtration by using a sand core funnel, discarding precipitates, carrying out spin drying on the obtained solution to obtain a dark yellow product, and putting the dark yellow product into a 55 ℃ oven for drying to obtain an intermediate.
S2, dissolving the intermediate (0.3695g,0.522mmol) and the 4,4 '-diamino-2, 2' -bipyridyl auxiliary ligand (0.0981g,0.528 mmol) in 45mL of methanol solvent by ultrasonic wave, adding ammonium hexafluorophosphate (0.8509g, 5.22mmol), stirring at room temperature for 2h, filtering off the precipitate, spin-drying the solvent, stir-frying with dichloromethane solvent, passing through a column, and eluting with petroleum ether, ethyl acetate, dichloromethane and acetone (the volume ratio of the four eluting reagents is 10:10:10:1) to obtain a yellow solid.
1.2 characterization
The yellow solid product obtained in 1.1 is subjected to1H NMR measurement, the structure is shown in FIG. 5, FIG. 5 is the product obtained in example 11H NMR test chart. As can be seen, the obtained product was an iridium complex [ Ir (ppy) having a structure represented by the formula (1)2(dabpy)]PF6。
Example 2
1.1 preparation
S1, adding F2bpy dichloro-bridge (1.0215g,0.838mmol) and silver hexafluorophosphate (0.464g,1.84mmol) were added to 70mL of methanol solvent, stirred at room temperature for 2h, filtered through a sand-core funnel, the precipitate was discarded, the resulting solution was spin-dried to give a dark yellow product, which was oven-dried at 55 ℃ to give an intermediate.
S2, ultrasonically dissolving the intermediate (0.4092g,0.522mmol) and the 4,4 '-diamino-2, 2' -bipyridyl auxiliary ligand (0.0981g,0.528 mmol) in 45mL of methanol solvent, then adding ammonium hexafluorophosphate (0.8509g, 5.22mmol), stirring at room temperature for 2h, filtering off precipitates, spin-drying the solvent, stir-frying a dichloromethane solvent, passing through a column, and eluting with petroleum ether, ethyl acetate, dichloromethane and acetone (the volume ratio of four eluting reagents is 10:10:10:1) to obtain a light yellow solid.
1.2 characterization
The yellow solid product obtained in 1.1 was characterized according to the characterization method in example 1, and the results are shown in FIG. 6, wherein FIG. 6 is the product obtained in example 21H NMR test chart. The results show that the obtained product is an iridium complex [ Ir (F) with a structure shown in a formula (1)2bpy)2(dabpy)]PF6。
Example 3
1.1 preparation
S1, adding tpy dichloro-bridge (0.9176g, 0.838mmol) and silver hexafluorophosphate (0.464g,1.84mmol) into 70mL of methanol solvent, stirring at room temperature for 2h, carrying out suction filtration by using a sand core funnel, discarding precipitates, carrying out spin drying on the obtained solution to obtain a dark yellow product, and putting the dark yellow product into a 55 ℃ oven for drying to obtain an intermediate.
S2, dissolving the intermediate (0.3758g, 0.522mmol) and the 4,4 '-diamino-2, 2' -bipyridyl auxiliary ligand (0.0981g,0.528 mmol) in 45mL of methanol solvent by ultrasonic wave, adding ammonium hexafluorophosphate (0.8509g, 5.22mmol), stirring at room temperature for 2h, filtering off the precipitate, spin-drying the solvent, stir-frying with dichloromethane solvent, passing through a column, and eluting with petroleum ether, ethyl acetate, dichloromethane and acetone (the volume ratio of the four eluting reagents is 10:10:10:1) to obtain a dark yellow solid.
1.2 characterization
The yellow solid product obtained in 1.1 was characterized by the characterization method in example 1, and the result showed that the obtained product was an iridium complex having a structure represented by formula (1) [ Ir (tpy)2(dabpy)]PF6。
Example 4
1.1 preparation
S1, adding the btp dichloro-bridge (1.0852g, 0.838mmol) and the silver hexafluorophosphate (0.464g,1.84mmol) into 70mL of methanol solvent, stirring at room temperature for 2h, carrying out suction filtration by using a sand core funnel, discarding the precipitate, carrying out spin drying on the obtained solution to obtain a dark yellow product, and putting the dark yellow product into an oven at 55 ℃ for drying to obtain an intermediate.
S2, ultrasonically dissolving the intermediate (0.428g, 0.522mmol) and the 4,4 '-diamino-2, 2' -bipyridyl auxiliary ligand (0.0981g,0.528 mmol) in 45mL of methanol solvent, then adding ammonium hexafluorophosphate (0.8509g, 5.22mmol), stirring at room temperature for 2h, filtering off the precipitate, spin-drying the solvent, stir-frying a dichloromethane solvent, passing through a column, and eluting with petroleum ether, ethyl acetate, dichloromethane and acetone (the volume ratio of four eluting reagents is 10:10:10:1) to obtain an orange solid.
1.2 characterization
The yellow solid product obtained in 1.1 was characterized by the characterization method in example 1, and the result showed that the obtained product was an iridium complex having a structure represented by formula (1) [ Ir (btp) ]2(dabpy)]PF6。
Example 5
1.1 preparation
S1, adding F2Adding ppy dichloro-bridge (1.0182g, 0.838mmol) and silver hexafluorophosphate (0.464g,1.84mmol) into 70mL of methanol solvent, stirring for 2h at room temperature, performing suction filtration by using a sand core funnel, discarding the precipitate, spin-drying the obtained solution to obtain a dark yellow product, and placing the dark yellow product into an oven at 55 ℃ for drying to obtain an intermediate.
S2, ultrasonically dissolving the intermediate (0.3883g, 0.522mmol) and the 4,4 '-diamino-2, 2' -bipyridyl auxiliary ligand (0.0981g,0.528 mmol) in 45mL of methanol solvent, then adding ammonium hexafluorophosphate (0.8509g, 5.22mmol), stirring at room temperature for 2h, filtering off precipitates, spin-drying the solvent, stir-frying a dichloromethane solvent, passing through a column, and eluting with petroleum ether, ethyl acetate, dichloromethane and acetone (the volume ratio of four eluting reagents is 10:10:10:1) to obtain a light yellow solid.
1.2 characterization
The yellow solid product obtained in 1.1 was characterized by the characterization method in example 1, and the result showed that the obtained product was an iridium complex [ IrF ] having a structure represented by formula (1)2ppy)2(dabpy)]PF6。
Example 6
1.1 preparation
K1, washing polypropylene (PP) nonwoven fabric with a thickness of 0.42mm in acetone, drying at 55 ℃, and packaging in an aluminum foil bag. The maleic anhydride solid was dissolved in tetrahydrofuran at room temperature to give a maleic anhydride solution (mass fraction 60%). Adding the maleic anhydride solution into an aluminum foil bag, completely immersing the solution into the polypropylene non-woven fabric, sealing the aluminum foil bag by heat molding, and placing the aluminum foil bag into a radiation field for irradiation. The irradiation conditions were: the dose rate is 25kGy/h and the total dose is 10kGy at room temperature. After irradiation, the non-woven fabric is taken out, washed by tetrahydrofuran and ethanol solvent in sequence by ultrasonic waves, and dried at the temperature of 55 ℃ to obtain the grafted material PP-g-MAH.
K2, preparation of the Metal Iridium Complex [ Ir (ppy) from example 12(dabpy)]PF6Dissolved in dioxane to obtain a complex solution (concentration of 0.8 g/L). And (3) putting the polypropylene non-woven fabric material grafted with maleic anhydride and having the diameter of 4cm into the complex solution, completely immersing the grafted non-woven fabric material in the solution, and carrying out reflux reaction at 110 ℃ for 9 hours. Then repeatedly ultrasonically cleaning the metal iridium-based composite material by using acetone, and drying the metal iridium-based composite material in vacuum at the temperature of 55 ℃ to obtain the metal iridium-based composite material PP-g-MAH-g- [ Ir (ppy)2(dabpy)]PF6。
1.2 characterization
The composite material obtained was subjected to XPS and EDS tests, and the results are shown in fig. 7, and fig. 7 is a XPS and EDS test chart of the product obtained in example 6. As can be seen, maleic anhydride molecules were grafted into the high molecular weight polymer, the metal iridium complex [ Ir (ppy)2(dabpy)]PF6Covalently linked to the maleic anhydride molecule. And a metal iridium complex [ Ir (ppy)2(dabpy)]PF6The distribution on the polymer substrate is relatively uniform.
1.3 photocatalytic hydrolysis experiment
4 pieces of the iridium-based composite material, 3 mu mol of potassium chloroplatinite, 20mL of triethylamine, 60mL of DMMF and 20mL of water are added into a photocatalyst system, a hydrogen production test is carried out under the illumination condition, hydrogen generated by the system directly enters a gas chromatography for on-line detection, the result is shown in figure 8, and figure 8 is a diagram of the photocatalytic hydrolysis hydrogen production effect of the iridium-based composite material obtained in example 6.
In fig. 8, the abscissa represents the time of the photocatalytic hydrolysis reaction, the left ordinate represents the hydrogen production amount, and the right ordinate represents TON ═ the number of moles of hydrogen produced × 2/moles of photosensitizer. It can be seen that the iridium-based composite material obtained in example 6 can continuously produce hydrogen for more than 300 hours in a photocatalytic system, and shows an ultra-long service life; and the composite material has excellent hydrogen production activity in an overlong using process.
Example 7
1.1 preparation
K1, washing polypropylene (PP) nonwoven fabric with a thickness of 0.42mm in acetone, drying at 55 ℃, and packaging in an aluminum foil bag. The maleic anhydride solid was dissolved in tetrahydrofuran at room temperature to give a maleic anhydride solution (mass fraction 60%). Adding the maleic anhydride solution into an aluminum foil bag, completely immersing the PP non-woven fabric in the solution, sealing the aluminum foil bag by heat molding, and placing the aluminum foil bag into a radiation field for irradiation. The irradiation conditions were: the dose rate is 25kGy/h and the total dose is 10kGy at room temperature. After irradiation, the material is taken out, washed by tetrahydrofuran and ethanol solvent in turn by ultrasonic, and dried at 55 ℃ to obtain the grafted material PP-g-MAH.
K2, preparation of the Metal Iridium Complex [ Ir (F) from example 22bpy)2(dabpy)]PF6Dissolved in dioxane to obtain a complex solution (concentration of 0.8 g/L). 4 pieces of PP non-woven fabric material grafted with maleic anhydride are put into the complex solution, so that the solution completely immerses the grafted solid material, and the reflux reaction is carried out for 9 hours at the temperature of 110 ℃. Then repeatedly ultrasonically cleaning the metal iridium-based composite material by using acetone, and drying the metal iridium-based composite material in vacuum at the temperature of 55 ℃ to obtain the metal iridium-based composite material PP-g-MAH-g- [ Ir (F)2bpy)2(dabpy)]PF6。
1.2 characterization
The resulting composite was tested according to the characterization method of example 1, and the results demonstrated that maleic anhydride molecules were grafted onto a high molecular weight polymer substrate material, a metal iridium complex [ Ir (F)2bpy)2(dabpy)]PF6Covalently linked to the maleic anhydride molecule.
1.3 photocatalytic hydrolysis experiment
4 pieces of the iridium-based composite material, 3 mu mol of potassium chloroplatinite, 20mL of triethylamine, 60mL of DMMF and 20mL of water are added into a photocatalyst system, a hydrogen production test is carried out under the illumination condition, hydrogen generated by the system directly enters a gas chromatograph to be detected on line, the result is shown in figure 9, and figure 9 is a diagram of the effect of photocatalytic hydrolysis hydrogen production of the iridium-based composite material obtained in example 7.
It can be seen that the iridium-based composite material obtained in example 7 can continuously produce hydrogen for over 300 hours in a photocatalytic system, and shows an ultra-long service life; and the composite material has excellent hydrogen production activity in an overlong using process.
Example 8
1.1 preparation
K1, washing polypropylene (PP) nonwoven fabric with a thickness of 0.42mm in acetone, drying at 55 ℃, and packaging in an aluminum foil bag. The maleic anhydride solid was dissolved in tetrahydrofuran at room temperature to give a maleic anhydride solution (mass fraction 60%). Adding the maleic anhydride solution into an aluminum foil bag, completely immersing the PP non-woven fabric in the solution, sealing the aluminum foil bag by heat molding, and placing the aluminum foil bag into a radiation field for irradiation. The irradiation conditions were: the dose rate is 25kGy/h and the total dose is 10kGy at room temperature. After irradiation, the material is taken out, washed by tetrahydrofuran and ethanol solvent in turn by ultrasonic, and dried at 55 ℃ to obtain the grafted material PP-g-MAH.
K2, preparation of the Metal Iridium Complex [ Ir (F) from example 52ppy)2(dabpy)]PF6Dissolved in dioxane to obtain a complex solution (concentration of 0.8 g/L). The maleic anhydride grafted PP nonwoven material with a diameter of 4cm was placed in the above complex solution to allow the solution to completely immerse the grafted solid material, and the reaction was carried out at 110 ℃ under reflux for 9 hours. Then repeatedly ultrasonically cleaning the metal iridium-based composite material by using acetone, and drying the metal iridium-based composite material in vacuum at the temperature of 55 ℃ to obtain the metal iridium-based composite material PP-g-MAH-g- [ Ir (F)2ppy)2(dabpy)]PF6。
1.2 characterization
The resulting composite was tested according to the characterization method of example 1, and the results demonstrated that maleic anhydride molecules were grafted onto a high molecular weight polymer substrate material, a metal iridium complex [ Ir (F)2ppy)2(dabpy)]PF6Covalently linked to the maleic anhydride molecule.
1.3 photocatalytic hydrolysis experiment
4 pieces of the iridium-based composite material, 3 mu mol of potassium chloroplatinite, 20mL of triethylamine, 60mL of DMMF and 20mL of water are added into a photocatalyst system, a hydrogen production test is carried out under the illumination condition, hydrogen generated by the system directly enters a gas chromatograph to be detected on line, the result is shown in figure 10, and figure 10 is a diagram of the effect of photocatalytic hydrolysis hydrogen production of the iridium-based composite material obtained in example 8.
It can be seen that the iridium-based composite material obtained in example 8 can continuously produce hydrogen for over 300 hours in a photocatalytic system, and shows an ultra-long service life; and the composite material has excellent hydrogen production activity in an overlong using process.
Example 9
1.1 preparation
K1, washing ultra-high molecular polyethylene fiber (UHMWPE) with diameter of 0.05mm in acetone, drying at 55 ℃, and packaging in aluminum foil bags. The maleic anhydride solid was dissolved in tetrahydrofuran at room temperature to give a maleic anhydride solution (mass fraction 60%). The maleic anhydride solution was added to the aluminum foil bag, the solution was allowed to completely submerge the UHMWPE fibers, the aluminum foil bag was sealed thermoplastically and placed in a radiation field for irradiation. The irradiation conditions were: the dose rate is 25kGy/h and the total dose is 10kGy at room temperature. After irradiation, the material is taken out, washed by tetrahydrofuran and ethanol solvent in turn by ultrasonic, and dried at 55 ℃ to obtain the graft material UHMWPE-g-MAH.
K2, preparation of the Metal Iridium Complex [ Ir (ppy) from example 12(dabpy)]PF6Dissolved in dioxane to obtain a complex solution (concentration of 0.8 g/L). Putting the UHMWPE fiber material grafted with the maleic anhydride into the complex solution, completely immersing the grafted solid material in the solution, and carrying out reflux reaction for 9 hours at 110 ℃. Then repeatedly ultrasonically cleaning the metal iridium-based composite material by using acetone, and drying the metal iridium-based composite material in vacuum at 55 ℃ to obtain UHMWPE-g-MAH-g- [ Ir (ppy)2(dabpy)]PF6。
1.2 characterization
The resulting composite was tested according to the characterization method of example 1, and the results demonstrated that maleic anhydride molecules were grafted to a high molecular weight polymer substrate material, a metal iridium complex [ Ir (ppy)2(dabpy)]PF6Covalently linked to the maleic anhydride molecule.
1.3 photocatalytic hydrolysis experiment
Adding 10 iridium-based composite materials, 3 mu mol of potassium chloroplatinite, 20mL of triethylamine, 60mLDMF and 20mL of water into a photocatalyst system, performing a hydrogen production test under the illumination condition, and directly feeding hydrogen generated by the system into a gas chromatography for online detection, wherein the result shows that the iridium-based composite material obtained in the example 9 can continuously produce hydrogen for more than 300 hours in the photocatalyst system and shows an ultra-long service life; and the composite material has excellent hydrogen production activity in an overlong using process.
Comparative example 1
A composite material was prepared by following the procedure of example 6 except that the metallic iridium complex [ Ir (ppy) in step K22(dabpy)]PF6Replacement by [ Ir (ppy)2(bpy)]PF6。
The hydrogen production effect of the composite material obtained by the photocatalytic hydrolysis test in example 6 was tested, and the result is shown in fig. 11, where fig. 11 is a graph of the hydrogen production effect of photocatalytic hydrolysis of the composite material obtained in comparative example 1. It can be seen that the iridium-based composite material obtained in comparative example 1 can continuously produce hydrogen for only 260 hours at most in a photocatalytic system, which is far lower than that of the examples, and the hydrogen production activity of the iridium-based composite material is obviously lower than that of the examples.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. A metallic iridium-based composite material, comprising:
the metal iridium complex comprises a high-molecular polymer solid-phase substrate material, maleic anhydride molecules grafted to the high-molecular polymer solid-phase substrate material and a metal iridium complex covalently connected with the maleic anhydride molecules;
the metal iridium complex has a structure shown in a formula (1):
Figure FDA0003059990090000011
wherein the content of the first and second substances,
Figure FDA0003059990090000012
one selected from the group consisting of the structures shown in formulas a to e:
Figure FDA0003059990090000013
the high molecular polymer in the high molecular polymer solid phase substrate material is selected from one or two of polypropylene and ultrahigh molecular polyethylene.
2. The composite material of claim 1, wherein the polymeric solid phase substrate material is a fiber, a nonwoven fabric or a porous film.
3. The composite material of claim 1, wherein the grafting density of the maleic anhydride on the high polymer solid substrate material is 15-75 nmol/cm2。
4. A preparation method of the metallic iridium-based composite material as claimed in any one of claims 1 to 3, which is characterized by comprising the following steps:
a) soaking a high molecular polymer solid phase substrate material in a solution of maleic anhydride, and performing irradiation grafting to obtain a high molecular solid phase substrate material grafted with maleic anhydride;
b) reacting the maleic anhydride grafted polymer solid phase substrate material with the metal iridium complex shown in the formula (1) in a solvent to obtain the metal iridium-based composite material covalently connected with the metal iridium complex shown in the formula (1).
5. The method of claim 4, wherein in step a):
the mass fraction of the maleic anhydride solution is 10-70%;
the radiation source of the irradiation grafting is a cobalt 60 source or an electron accelerator;
the dose of the irradiation grafting is 5-100 kGy, and the dose rate is 0.3-5 kGy/h.
6. The method of claim 4, wherein the step b) comprises:
b1) dissolving a metal iridium complex shown in a formula (1) in a solvent to obtain a metal iridium complex solution;
b2) soaking the maleic anhydride grafted polymer solid phase substrate material in the metal iridium complex solution for reaction to obtain a metal iridium-based composite material covalently connected with the metal iridium complex in the formula (1);
the concentration of the metal iridium complex solution is 0.5-1.5 g/L;
the reaction temperature is 100-120 ℃, and the reaction time is 8-12 h.
7. The method according to claim 4, wherein the step a), after the irradiation grafting, further comprises: cleaning and drying;
in the step b), after the reaction, the method further comprises: and (4) cleaning and drying.
8. A method of photocatalytic hydrolysis, comprising:
under the action of a photosensitizer, the photocatalytic system is hydrolyzed to generate hydrogen;
the photocatalytic system comprises a catalyst, a sacrificial agent, and water;
the photosensitizer is the metallic iridium-based composite material as defined in any one of claims 1 to 3.
9. The method of claim 8, wherein the catalyst comprises potassium chloroplatinite, [ Co (bpy)3]Cl2And [ Rh (dtbbpy)](PF6)2One or more of the above;
the sacrificial agent is triethylamine and/or triethanolamine.
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