CN108080036B - Hybrid material based on photosensitive metal-organic coordination nanocage and titanium dioxide and preparation method and application thereof - Google Patents
Hybrid material based on photosensitive metal-organic coordination nanocage and titanium dioxide and preparation method and application thereof Download PDFInfo
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- CN108080036B CN108080036B CN201711107551.8A CN201711107551A CN108080036B CN 108080036 B CN108080036 B CN 108080036B CN 201711107551 A CN201711107551 A CN 201711107551A CN 108080036 B CN108080036 B CN 108080036B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000000463 material Substances 0.000 title claims abstract description 85
- 239000002091 nanocage Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 33
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
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- 239000007787 solid Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- 238000003917 TEM image Methods 0.000 description 2
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- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 2
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- ABMYEXAYWZJVOV-UHFFFAOYSA-N pyridin-3-ylboronic acid Chemical compound OB(O)C1=CC=CN=C1 ABMYEXAYWZJVOV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- QJZUKDFHGGYHMC-UHFFFAOYSA-N pyridine-3-carbaldehyde Chemical compound O=CC1=CC=CN=C1 QJZUKDFHGGYHMC-UHFFFAOYSA-N 0.000 description 1
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- ARYHTUPFQTUBBG-UHFFFAOYSA-N thiophen-2-ylboronic acid Chemical compound OB(O)C1=CC=CS1 ARYHTUPFQTUBBG-UHFFFAOYSA-N 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
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- 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
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Abstract
The invention discloses a hybrid material based on a photosensitive metal-organic coordination nanocage and titanium dioxide, and a preparation method and application thereof. The hybrid material based on the photosensitive metal-organic coordination nanocages and the titanium dioxide comprises the photosensitive metal-organic coordination nanocages and the titanium dioxide. Also discloses a preparation method of the hybrid material based on the photosensitive metal-organic coordination nanocage and titanium dioxide and the application of the hybrid material in photocatalysis. The organic-inorganic hybrid material prepared from the photosensitive metal-organic coordination nanocage and the titanium dioxide has a hierarchical porous structure, and can improve free diffusion of gas and CO2The surface adsorption increases the reactant adsorption capacity and the activation degree, and can also reduce the recombination probability of electron-hole pairs and effectively improve the photocatalysis efficiency.
Description
Technical Field
The invention relates to a hybrid material based on a photosensitive metal-organic coordination nanocage and titanium dioxide, and a preparation method and application thereof.
Background
Due to the energy crisis and environmental pollution problems in the present society, the demand of people for new clean and efficient energy is increasingly urgent. Solar energy attracts people's attention because of its advantages of being green, efficient, abundant and renewable. The conversion of solar energy into chemical energy for utilization also becomes the focus of research. Photocatalytic water decomposition to generate hydrogen and oxygen, or hydrogen generation and oxygen transfer in water to oxidize organic substrates have become a research hotspot. The carbon dioxide gas is reduced by photocatalysis to generate carbon monoxide or other organic micromolecules, so that the problem of carbon dioxide pollution is solved, micromolecule energy substances are obtained, and the method has wide application prospect.
The metal-organic coordination cage has definite structural characteristics, a rigid framework and a confined cavity, and the characteristics endow the metal-organic coordination cage with various excellent functions. Which are themselves self-assembled from a wide variety of functionalized, structured organic ligands and inorganic metal ion complexes. The organic ligand can select organic molecules with photosensitive capability, so that the metal nanocage has light absorption capability, and the metal center can select metal ions with photo-oxidation-reduction activity to be used as an active site for catalytic reaction. The cage constructed by the two can enable a plurality of photosensitive groups and the metal catalytic center to be more tightly combined, and is beneficial to the transmission of electrons between molecules. However, most of the existing metal-organic coordination cages are homogeneous catalytic reactions, and the continuous hydrogen production capability of the metal-organic coordination cages is insufficient, and the photocatalytic stability is low.
TiO2Is a wide band gap semiconductor with wide source, easy preparation, environmental protection, harmlessness and stable property, and can be used for preparing hydrogen by photocatalytic reduction of water and for photocatalytic reduction of CO2Has important application prospect. But the biggest problem is that the catalyst is only active under ultraviolet rays, cannot utilize the visible light part which accounts for most of the solar energy, and has great influence on the catalytic efficiency. Thus, a number of different approaches have been used to treat TiO2Modified to broaden its absorption spectrum. The common solution at present is surface modification or ion doping, however, the surface modification easily causes problems of competitive adsorption, active site occupation and the like, and the ion doping introduces a large number of electron-hole recombination centers, which results in reduction of catalytic activity and stability of the photocatalyst.
Compared with the traditional composite material, the hybrid material is combined on a more microscopic nanometer or even molecular level, and can bring more new characteristics and performances. Organic metal nano cage with specific function and TiO2The inorganic material is combined on the nanometer or even molecular scale by a proper method, and a novel functional material, namely a metal-organic coordination nanocage/TiO with more excellent performance can be obtained2A hybrid material.
Disclosure of Invention
The invention aims to provide a hybrid material based on photosensitive metal-organic coordination nanocages and titanium dioxide, a preparation method thereof and application thereof in photocatalysis.
The technical scheme adopted by the invention is as follows:
a hybrid material based on a photosensitive metal-organic coordination nano cage and titanium dioxide comprises the photosensitive metal-organic coordination nano cage and the titanium dioxide, wherein the general structural formula of the photosensitive metal-organic coordination nano cage is at least one of a formula (I), a formula (II) and a formula (III);
formula (I) [ M6(RuL3)8](X)28；
M of formula (II)12(L)24(X)24；
M of the formula (III)2(L)4(X)4；
Wherein, L is a photosensitive ligand, and in the formula (I), L is
In the formula (II) are
In formula (III) is
The R substituents in the formulae (II) and (III) are-OH, -COOH, -NH2、-NH(CH2)nCH3、
or-NHCOO (CH)2)nCH3N is 0 to 6;
m is metal ion, Pd in formula (I), (II) or (III)2+Or Pt2+At least one of;
x is a counter anion, BF in formula (I), (II) or (III)4 -、NO3 -Or PF4 -At least one of (1).
In the hybrid material, the photosensitive metal-organic coordination nanocage accounts for 1-10% of the mass of the titanium dioxide.
A preparation method of a hybrid material based on photosensitive metal-organic coordination nanocages and titanium dioxide comprises the following steps:
1) preparing a photosensitive metal-organic coordination nanocage solution: dissolving a photosensitive metal-organic coordination nanocage in an organic solvent to prepare a photosensitive caging solution;
2) photosensitive metal-organic coordination nanocage-TiO2Preparation of gel: mixing tetrabutyl titanate, chelating agent, water and photosensitive cage solution, heating the mixed solution to solidify to form semitransparent colloidal solid, and obtaining photosensitive cage-TiO2Gelling;
3) post-treatment of the gel: extraction of photoactive cage-TiO2And (4) gelling and drying to obtain the hybrid material based on the photosensitive metal-organic coordination nanocages and titanium dioxide.
In the preparation method of the hybrid material, in step 1), the organic solvent is at least one of THF, DMF, DMSO, methanol and ethanol.
In the preparation method of the hybrid material, in the step 1), the concentration of the photosensitive metal-organic coordination nanocages in the photosensitive cage solution is (1-10) mu mol/L.
In the step 2) of the preparation method of the hybrid material, the volume ratio of tetrabutyl titanate, the chelating agent, water and the photosensitive cage solution is 1: (0.1-0.3): (0.1-0.3): (1-2).
In the step 2) of the preparation method of the hybrid material, the chelating agent is glacial acetic acid.
The preparation method of the hybrid material comprises the step 2), wherein the heating temperature is 50-70 ℃, and the heating time is 20-30 h.
In the step 3) of the preparation method of the hybrid material, the extraction method is Soxhlet extraction.
A photocatalyst comprises the hybrid material based on the photosensitive metal-organic coordination nanocage and titanium dioxide.
The invention has the beneficial effects that:
the organic-inorganic hybrid material prepared from the photosensitive metal-organic coordination nanocage and the titanium dioxide has a hierarchical porous structure, and can improve free diffusion of gas and CO2The surface adsorption increases the reactant adsorption capacity and the activation degree, and can also reduce the recombination probability of electron-hole pairs and effectively improve the photocatalysis efficiency.
The method comprises the following specific steps:
1. the hybrid material prepared by the method has a pure anatase crystal form and has high catalytic activity;
2. photosensitive metal-organic coordination nanocage and TiO2The precursor tetrabutyl titanate is fully mixed in the material structure construction stage, and the photosensitive cage contains a plurality of carboxyl, pyridine, amino, amide or hydroxyl which can be mixed with TiO2The skeleton forms a compact cross-linked structure and has good firmness, so that the stability of the material is improved;
3. the photosensitive cage has good light absorption performance, light excitation performance and high-efficiency electron injection capability, and the cage structure can form a large number of pore channels in the hybrid material, so that the internal surface area of the material is improved, more active sites and reaction sites are provided, and the photocatalytic capability is good;
4. the photosensitive cage carries cocatalyst metals such as palladium and platinum metals, and does not need to additionally load metal nanoparticles for photocatalytic hydrogen production, after the hybrid material is prepared, a photosensitive group, a metal catalytic center and a semiconductor are tightly combined into a whole, so that the transfer of electrons among molecules is facilitated, and the stability of the catalytic material is improved; and Re catalytic center can be loaded on the hybrid material, and hydrogen is produced by decomposing water and CO is converted simultaneously under the catalysis of visible light2To CO to produce synthesis gas.
Drawings
FIG. 1 is a schematic diagram of the structural formula of the compound of formula (I);
FIG. 2 is a schematic representation of the structural formula of the compound of formula (II);
FIG. 3 is a schematic diagram of the structural formula of the compound of formula (III);
FIG. 4 is a schematic of the structural formula of MOC-2 compound;
FIG. 5 is a schematic diagram of the synthetic route of the photoactive cage MOC-1;
FIG. 6 is a schematic diagram of MOC-1 synthesis from compounds 1-3;
FIG. 7 shows the photo-sensitive cage MOC-1 in DMSO-d6/D2Hydrogen spectrum in O (v: v ═ 1:2) solvent;
FIG. 8 shows the photo-sensitive cage MOC-1 in DMSO-d6/D2O (v: v ═ 1:2) solvent1H-1H COSY spectrogram;
FIG. 9 shows a photo-sensitive cage MOC-1-TiO2Transmission electron microscopy of the hybrid material;
FIG. 10 shows a photo-sensitive cage MOC-1-TiO2The ultraviolet-visible absorption spectrum of the hybrid material;
FIG. 11 shows a photo-sensitive cage MOC-1-TiO277K nitrogen adsorption and desorption curve diagram of the hybrid material;
FIG. 12 is MOC-1-TiO2A hydrogen production result diagram of water photocatalytic decomposition by the visible light of the hybrid material;
FIG. 13 is ReP @ MOC-1-TiO2Visible light photoreduction of CO by material2Converting a CO result graph;
FIG. 14 is ReP @ MOC-1-TiO2The result chart of CO-hydrogen production and CO production by visible light photocatalysis of the material;
FIG. 15 is a schematic diagram of the synthetic route of the photoactive cage MOC-2;
FIG. 16 is a schematic of the synthesis of MOC-2 from compound 2-4;
FIG. 17 is MOC-2-TiO2Scanning electron micrographs of the hybrid material;
FIG. 18 is MOC-2-TiO2Transmission electron microscopy of the hybrid material;
FIG. 19 is MOC-2-TiO277K nitrogen adsorption and desorption curve diagram of the hybrid material;
FIG. 20 is MOC-2-TiO2A hydrogen production result diagram by photocatalytic decomposition of water with the visible light of the hybrid material.
Detailed Description
A hybrid material based on a photosensitive metal-organic coordination nano cage and titanium dioxide comprises the photosensitive metal-organic coordination nano cage and the titanium dioxide, wherein the general structural formula of the photosensitive metal-organic coordination nano cage is at least one of a formula (I), a formula (II) and a formula (III); the structural formula schematic diagrams of the compounds of formula (I), formula (II) and formula (III) are respectively shown in the attached drawings 1, 2 and 3;
wherein, L is a photosensitive ligand, and in the formula (I), L is
In the formula (II) are
In formula (III) is
The R substituents in the formulae (II) and (III) are-OH, -COOH, -NH2、-NH(CH2)nCH3、
or-NHCOO (CH)2)nCH3N is 0 to 6;
m is metal ion, Pd in formula (I), (II) or (III)2+Or Pt2+At least one of;
x is a counter anion, BF in formula (I), (II) or (III)4 -、NO3 -Or PF4 -At least one of (1).
Preferably, the structure of the photosensitive metal-organic coordination nanocage is one of the following structures:
a compound of the structure of formula (i) shown in fig. 1, wherein M ═ Pd2+，
X＝BF4 -(ii) a Or a compound of the structure shown in figure 4.
In the hybrid material, the photosensitive metal-organic coordination nanocage accounts for 1-10% of the mass of the titanium dioxide.
A preparation method of a hybrid material based on photosensitive metal-organic coordination nanocages and titanium dioxide comprises the following steps:
1) preparing a photosensitive metal-organic coordination nanocage solution: dissolving a photosensitive metal-organic coordination nanocage in an organic solvent to prepare a photosensitive caging solution;
2) photosensitive metal-organic coordination nanocage-TiO2Preparation of gel: mixing tetrabutyl titanate, chelating agent, water and photosensitive cage solution, heating the mixed solution to solidify to form semitransparent colloidal solid, and obtaining photosensitive cage-TiO2Gelling;
3) post-treatment of the gel: extraction of photoactive cage-TiO2And (4) gelling and drying to obtain the hybrid material based on the photosensitive metal-organic coordination nanocages and titanium dioxide.
Preferably, in step 1) of the preparation method of the hybrid material, the organic solvent is at least one of THF, DMF, DMSO, methanol, and ethanol.
Preferably, in the step 1) of the preparation method of the hybrid material, the concentration of the photosensitive metal-organic coordination nanocages in the photosensitive cage solution is (1-10) mu mol/L.
Preferably, in step 2) of the preparation method of the hybrid material, the volume ratio of tetrabutyl titanate, the chelating agent, water and the photocage solution is 1: (0.1-0.3): (0.1-0.3): (1-2).
Preferably, in step 2) of the preparation method of the hybrid material, the chelating agent is glacial acetic acid.
Preferably, in the step 2) of the preparation method of the hybrid material, the heating temperature is 50-70 ℃ and the heating time is 20-30 h.
Preferably, in step 3), the extraction method is soxhlet extraction.
A photocatalyst comprises the hybrid material based on the photosensitive metal-organic coordination nanocage and titanium dioxide.
Further, the photocatalyst is a catalyst for hydrogen production by photolysis of water and photocatalytic reduction of CO2Catalyst, photocatalytic synthesis of H2At least one of the catalysts is/CO.
Preferably, a photocatalytic reduction of CO2Catalyst or photocatalytic synthesis of H2the/CO catalyst comprises a hybrid material based on photosensitive metal-organic coordination nano cage and titanium dioxide and a rare metal complex; further preferably, the rare metal complex is a Re complex.
The present invention will be described in further detail with reference to specific examples.
In the examples, the conditions of the tests for the application of the photocatalysis are illustrated below:
photolysis water hydrogen production and hydrogen production amount determination test
Adding 50mg of hybrid material, 90mL of distilled water and 10mL of triethanolamine into a quartz reactor matched with a photocatalytic system, covering a cover, connecting the photocatalytic system, checking the airtightness, then carefully opening a valve while stirring to vacuumize, carefully controlling the vacuum degree to prevent the solvent from bumping, closing an evacuation valve after the solvent is pumped to an equilibrium state, irradiating reaction liquid by using a xenon lamp (with a filter, a cut-off type, more than 420nm), sampling every 1h, and measuring the hydrogen yield by using GC.
Photocatalytic reduction of CO2Conversion to CO determination test
Adding 10mg of hybrid material, 5mL of DMF and 134mg of 1, 3-dimethylbenzimidazole into a 40mL quartz reaction bottle, sealing with a polytetrafluoroethylene bottle cap matched with a silica gel gasket, vacuumizing and filling nitrogen for 15min for three times respectively, and blowing CO2After 30min, the reaction solution was irradiated with a xenon lamp (with a filter, cut-off, > 420nm), sampled at regular intervals, and the CO production was determined by chromatography.
Simultaneous photocatalytic hydrogen production and CO reduction2Conversion to CO determination test
Adding 10mg of hybrid material, 3mL of DMF, 2mL of water and 134mg of 1, 3-dimethyl benzimidazole into a 40mL quartz reaction bottle, sealing with a polytetrafluoroethylene bottle cap matched with a silica gel gasket, vacuumizing and filling nitrogen for 15min for three times respectively, and blowing CO2After 30min, the reaction solution was irradiated with a xenon lamp (with a filter, cut-off, > 420nm), sampled at regular intervals, and the hydrogen production and CO production were measured by chromatography.
Example 1:
synthesis of photosensitive metal-organic coordination nanocage MOC-1
The synthetic route of the photosensitive metal-organic coordination nanocage MOC-1 is shown in the attached figure 5. The schematic diagram shows only an example of the synthesis method, and the method of the present invention is not limited to the relevant substances shown in the figure. The specific synthesis steps are as follows:
1. synthesis of Compound 1-2
The synthesis steps are as follows: in a 100mL round-bottom flask were placed 1.206g (11.2mmol) of pyridine-3-carbaldehyde, 1.974g (9.4mmol) of 1, 10-phenanthroline-5, 6-dione (1-1), 14.48g (188mmol) of ammonium acetate and 40mL of glacial acetic acid, the reaction mixture was refluxed for 3 hours, cooled to room temperature after completion of the reaction, and diluted with 160mL of distilled water. Dropwise adding strong ammonia water into the diluted reaction solution, continuously stirring until a large amount of yellow precipitate is generated, carrying out suction filtration, washing with water to obtain a crude product, and recrystallizing the crude product with ethanol to obtain 2.7g of the crude product, wherein the yield is 90%. IR (KBr pellet, cm)-1)：3036s,1677m,1607m,1506m,1468m,1423m,1396m,1296w,1071m,1026m,952w,813m,738s,709s,672m。1HNMR(DMSO-d6，25℃，，ppm)：9.52(d，J＝1.9Hz，1H)，9.47(d，J＝1.8H，1H)，9.06(dd，J＝4.3Hz，1.5Hz，2H)，8.91(d，J＝6.8Hz)，8.72(dd，J＝4.7Hz，1.4Hz，1H)，8.60(dt，J＝8.0Hz，1.7Hz，1H)，7.86(br，2H)，7.67(q，J＝4.6Hz)。
2. Synthesis of Compounds 1-3
The synthesis steps are as follows: a50 mL round bottom flask was charged with 260mg RuCl3·3H2O (2mmol) and 891mg of compound 1-2(3mmol), and finally 20mL of ethylene glycol was added as a reaction solvent. The reaction is carried out under microwave conditions (400W, 190 ℃), the reaction is stopped after 10min, the reaction solution is cooled, poured into 60mL of distilled water, and saturated KPF is added dropwise under stirring6Saturating the solution, separating out a large amount of orange red solid from the reaction solution, continuing stirring for 0.5h, and performing suction filtration to obtain orange redThe colored solid was washed with water and dried. The crude product was extracted with 500mL acetone, the insolubles were filtered and the filtrate was spin dried to give about 500mg of product in 65% yield. IR (KBr pellet, cm)-1)：1628m，1429m，1383m，1159m，1059m，1026m，867m，561w.1HNMR(DMSO-d 625 ℃, ppm): 9.52(d, J ═ 1.9Hz,1H),9.11(d, J ═ 8.1Hz,2H),8.81(dd, J ═ 4.9,1.5Hz,1H),8.66(dt, J ═ 8.1Hz,1.9Hz,1H),8.14(d, J ═ 5.0Hz,2H),7.93(br,2H),7.78-7.70(dd, J ═ 8.2Hz,4.9Hz, 1H). Elemental analysis: RuL3(BF4)2·5H2O(C54H33B2F8N15Ru·5H2O) theoretical value (%): c, 51.61; h, 3.45; n,16.72. experimental values (%): c, 51.68; h, 3.42; n, 16.26.
3. Synthesis of photosensitive cage MOC-1
A schematic diagram of MOC-1 synthesis from compounds 1-3 is shown in FIG. 6.
The synthesis steps are as follows: 0.1mmol of the compound 1-3 and 0.075mmol of PdX2(X＝BF4 -) Dissolving in 5mL of DMSO, stirring and heating to 80 ℃ for reaction for 8h, adding 30mL of ethyl acetate after the reaction is finished, separating out a large amount of orange flocculent solid precipitate, centrifuging, washing the solid with a small amount of acetone, and drying in vacuum to obtain a solid product with the yield of about 70%. Elemental analysis: [ Pd6(RuL3)8](BF4)28·(H2O)108Theoretical value (%): c, 40.04, H, 3.73, N, 12.97; experimental values (%): c, 39.90, H, 3.49, N, 12.56. Photosensitive cage MOC-1 in DMSO-d6/D2The hydrogen spectrum of O (v: v ═ 1:2) solvent is shown in figure 7, and it is1H-1The H COSY spectrum is shown in figure 8.
Di, hybridized material MOC-1-TiO2Preparation of
168 μ L of glacial acetic acid, 106 μ L of distilled water, 1mL of tetrabutyltitanate and 2mL of a solution of MOC-1(12.5mg) in DMF were added in succession to a 20mL sample vial, the mixture was left to stand open, heated at 70 ℃ for 2h and then at 50 ℃ overnight to form a deep red gelatinous solid, which was ground and subjected to Soxhlet extraction for 48h and then dried under vacuum overnight to give a dark brown powder. FIG. 9 shows a hybrid MOC-1-TiO2Transmission electron micrograph (D). FIG. 10 shows a hybrid MOC-1-TiO2The ultraviolet visible absorption spectrum shows that the material has stronger absorption in a visible light region. FIG. 11 shows a hybrid MOC-1-TiO277K nitrogen adsorption and desorption graph, and the BET specific surface area of the material is 285m as can be analyzed from FIG. 112(ii)/g, contains a nano-scale porous structure.
III, hybrid material MOC-1-TiO2Results of hydrogen production
Under the condition of not loading a promoter Pt particle, on a material MOC-1-TiO2The hydrogen production performance and stability are tested, and the result shows that the hydrogen production rate is 4 mmol/g in 10mL triethanolamine and 90mL water under the irradiation of visible light (lambda is more than or equal to 420nm)-1·h-1(see MOC-1-TiO of FIG. 122A hydrogen production result diagram by photocatalytic decomposition of water with visible light of the hybrid material).
Hybrid photocatalytic material Re @ HO-TPA/TiO loaded by tetra-Re complex2Preparation of
The structures of the Re complex and the electron donor BIH used in the experimental process are as follows:
Re@HO-TPA/TiO2the preparation process comprises the following steps: 20mg of MOC-1-TiO are taken2Adding into 1mL of distilled water, ultrasonically dispersing for 5min, vacuumizing and filling argon for three times respectively, dropwise adding 0.40mL of 0.448mM ReP aqueous solution, stirring for 3h, centrifuging and precipitating, washing with distilled water for 3 times, and vacuumizing at room temperature overnight.
Penta, Re @ MOC-1-TiO2Photocatalytic reduction of CO2Performance of
For Re @ HO-TPA/TiO2Photocatalytic reduction of CO from materials2The activity was tested in saturated CO2In pure DMF, 134mg of BIH as an electron donor and 10mg of a photocatalyst ReP @ HO-TPA/TiO under the condition of visible light (lambda is more than or equal to 420nm)2The TON of CO production at 20 hr was 1200, see ReP @ MOC-1-TiO of FIG. 132Photocatalytic reduction of CO2And (5) a result chart.
Six, Re @ MOC-1-TiO2Photocatalytic synthesis of H2Performance of CO
For ReP @ MOC-1-TiO2Photocatalytic simultaneous production of hydrogen and reduction of CO from materials2The activity was tested in saturated CO2In 4mL of DMF and 1mL of water, 134mg of BIH as an electron donor, and 10mg of photocatalyst ReP @ HO-TPA/TiO under the condition of visible light (lambda is more than or equal to 420nm)2The TON of CO produced in 42 hr is 1849, while the TON of hydrogen produced in 1590, see ReP @ MOC-1-TiO in FIG. 142The result of CO-producing hydrogen and CO by visible light photocatalysis of the material is shown in the figure.
Example 2:
synthesis of photosensitive metal-organic coordination nanocage MOC-2
The synthetic route of the photosensitive metal-organic coordination nanocage MOC-2 is shown in the attached figure 15. The schematic diagram shows only an example of the synthesis method, and the method of the present invention is not limited to the relevant substances shown in the figure. The specific synthesis steps are as follows:
1. synthesis of Compound 2-2
Tribromotriphenylamine 2-1(2.4g, 5mmol), 2-thiopheneboronic acid (3.5g, 30mmol) were dissolved in 100mL THF; anhydrous potassium carbonate (12g, 85mmol) was dissolved in 40mL of water; the above solution was mixed in a 250mL Schlenk flask, purged with argon to remove oxygen for 1h, and Pd (pph) under argon atmosphere3)4(1.3g, 1.1mmol) was added to a Schlenk flask, heated to 70 ℃ for condensation reflux for 6h, after the reaction was completed, the reaction solution was cooled and spin-dried, dissolved in dichloromethane, filtered, the filtrate was washed with ammonia water and water in sequence, the organic phase was left to dry over anhydrous sodium sulfate, filtered and spin-dried. Column chromatography (petroleum ether: dichloromethane ═ 15:1) gave 2.3g (compound 2-2) of a grey solid in 95% yield. MALDI-TOF M/z 491([ M + H)]+)。
2. Synthesis of Compounds 2-3
Dissolving the compound 2-2(2.3g, 4.7mmol) in 20mL DMF, adding NBS (2.5g, 14.1mmol) under ice bath condition, reacting for 1h away from light, adding a large amount of distilled water after the reaction solution is solidified, and filtering and washing to obtain a dark yellow solid 2-32.3g with the yield of 70%.1H NMR(400MHz,CDCl3)8.01(s,1H),7.41(d,J＝8.3Hz,3H),7.11(d,J＝8.3Hz,3H),7.00(d,J＝9.2Hz,3H).MALDI-TOF:m/z 729.300([M+H]+)。
3. Synthesis of Compounds 2-4
Compound 2-3(2.3g, 3.3mmol), 3-pyridineboronic acid (2.4g, 19.8mmol) were dissolved in 100mL DMF, anhydrous potassium carbonate (8g, 56.1mmol) was dissolved in 20mL water, the above solution was mixed in a 250mL Schlenk flask, argon was passed through to remove oxygen for 1h, and Pd (pph) was added under argon atmosphere3)4(0.84g, 0.73mmol) was added to a Schlenk flask, heated to 100 ℃ for condensation reflux for 12h, after the reaction was completed, cooled, the reaction solution was spin-dried, dissolved with dichloromethane, filtered, the filtrate was washed with ammonia water and water in sequence, the organic phase was left, dried over anhydrous sodium sulfate, filtered and spin-dried. Column chromatography (ethyl acetate: petroleum ether ═ 4: 1) gave 2-41.2 g of a brown solid in 50.3% yield.1H NMR(400MHz,DMSO-d6)8.94(s,1H),8.50(d,J＝4.7Hz,1H),8.08(d,J＝8.0Hz,1H),7.70(d,J＝7.7Hz,3H),7.54(d,J＝3.8Hz,1H),7.46(dd,J＝8.0,4.8Hz,1H),7.16(d,J＝8.3Hz,2H)。MALDI-TOF:722.688，m/z([M+H]+)。
4. Synthesis of photosensitive cage MOC-2
A schematic diagram of MOC-2 synthesis from compounds 2-4 is shown in FIG. 16.
Weighing palladium tetrafluoroborate (44mg, 0.1mmol) and dissolving in 1mL of DMSO solution, dissolving compound 2-4(144mg, 0.2mmol) in 9mL of DMSO solution, respectively stirring and heating to 60 ℃, mixing the two solutions after the two solutions are clarified, stirring for 30min at 60 ℃, cooling, adding 80mL of ethyl acetate for recrystallization, centrifuging, and performing vacuum pumping at normal temperature to obtain a yellow solid MOC-2110 mg with a yield of 63%.1H NMR(400MHz,DMSO-d6)9.49(s,1H),9.03(s,1H),8.95(s,1H),8.52(d,J＝6.1Hz,2H),8.10(s,1H),7.87-7.43(m,15H),7.37(s,1H),7.16(d,J＝8.2Hz,1H),6.99(d,J＝9.0Hz,3H).ESI-Q-TOF:M/Z 1063.4891[M3+]；M/Z 775.8658[M4+]。
Di, hybridized material MOC-2-TiO2Preparation of
Weighing photosensitive cage MOC-212.5 mg, dissolving in 1mL DMSO, adding 168 μ L glacial acetic acid, 106 μ L distilled water and 1mLDMSO into a 20mL sample bottle, opening the sample bottle, heating and stirring at 60 ℃, then slowly dropwise adding 1mL tetrabutyl titanate and 1mL DMSO solution of photosensitive cage MOC-2(12.5mg) respectively, and heating at 60 ℃ for 26h to obtain a dark red gelatinous solid. Taking out the gel, performing Soxhlet extraction at 140 ℃ for 72h, taking out the gel, and drying at 60 ℃ to obtain reddish brown powder. FIG. 17 hybrid material MOC-2-TiO2FIG. 18 shows a hybrid MOC-2-TiO2Transmission electron micrograph (D). FIG. 19 shows a hybrid MOC-2-TiO277K nitrogen adsorption and desorption curve, the BET specific surface area of the material can be analyzed to be 215m from FIG. 192(ii)/g, contains a nano-scale porous structure.
Three, photocatalytic material MOC-2-TiO2Hydrogen production Performance test
In a hybrid material MOC-2-TiO2The hydrogen production performance of the material is tested under the condition of not loading Pt particles, and the result shows that the hydrogen production efficiency of 50mg of hybrid material in 10mL of triethanolamine and 90mL of water is about 4 mmol/g under the irradiation of visible light (lambda is more than or equal to 420nm)-1h-1(see FIG. 20).
The hybrid material can be used for producing hydrogen by decomposing water under the catalysis of visible light without loading Pt catalytic particles, and has excellent performance and stability. After loading Re catalyst, CO is catalytically reduced in a solvent without water in visible light2Can stably, efficiently and selectively react CO in experiments2Conversion to CO; in a solvent containing water, hydrogen can be produced by decomposing water and converting CO simultaneously under the catalysis of visible light2Is CO, wherein H2The volume ratio of/CO (synthesis gas) can be adjusted by varying the water content.
Claims (10)
1. A hybrid material based on photosensitive metal-organic coordination nanocages and titanium dioxide is characterized in that: the composite material comprises a photosensitive metal-organic coordination nano cage and titanium dioxide, wherein the general structural formula of the photosensitive metal-organic coordination nano cage is at least one of formula (I) and formula (II);
formula (I) [ M6(RuL3)8](X)28；
M of formula (II)12(L)24(X)24；
Wherein, L is a photosensitive ligand;
in formula (I), RuL3Is composed of
；
In the formula (II), L is
；
The R substituent in the formula (II) is-OH, -COOH or-NH2、-NH (CH2)nCH3、
、
or-NHCOO (CH)2)nCH3N =0 to 6;
m is metal ion, and Pd is shown in formula (I) or (II)2+Or Pt2+At least one of;
x is counter anion, BF in formula (I) or (II)4 -、NO3 -Or PF4 -At least one of (1).
2. The hybrid material based on photosensitive metal-organic coordination nanocages and titanium dioxide as claimed in claim 1, wherein: the photosensitive metal-organic coordination nanocage accounts for 1-10% of the mass of the titanium dioxide.
3. A preparation method of a hybrid material based on a photosensitive metal-organic coordination nanocage and titanium dioxide is characterized by comprising the following steps: the method comprises the following steps:
1) preparing a photosensitive metal-organic coordination nanocage solution: dissolving a photosensitive metal-organic coordination nanocage in an organic solvent to prepare a photosensitive caging solution;
2) photosensitive metal-organic coordination nanocage-TiO2Preparation of gel: mixing tetrabutyl titanate, chelating agent, water and photosensitive cage solution, heating the mixed solution to solidify to form semitransparent colloidal solid, and obtaining photosensitive cage-TiO2Gelling;
3) post-treatment of the gel: extraction of photoactive cage-TiO2Gelling and drying to obtain the hybrid material based on the photosensitive metal-organic coordination nanocage and the titanium dioxide of claim 1.
4. The preparation method of the hybrid material based on the photosensitive metal-organic coordination nanocage and the titanium dioxide as claimed in claim 3, wherein the preparation method comprises the following steps: in the step 1), the organic solvent is at least one of THF, DMF, DMSO, methanol and ethanol.
5. The preparation method of the hybrid material based on the photosensitive metal-organic coordination nanocage and the titanium dioxide as claimed in claim 4, wherein the preparation method comprises the following steps: in the step 1), the concentration of the photosensitive metal-organic coordination nanocages in the photosensitive cage solution is (1-10) mu mol/L.
6. The preparation method of the hybrid material based on the photosensitive metal-organic coordination nanocage and the titanium dioxide as claimed in claim 3, wherein the preparation method comprises the following steps: in the step 2), the volume ratio of tetrabutyl titanate, the chelating agent, water and the photosensitive cage solution is 1: (0.1-0.3): (0.1-0.3): (1-2).
7. The preparation method of the hybrid material based on the photosensitive metal-organic coordination nanocage and the titanium dioxide as claimed in claim 6, wherein the preparation method comprises the following steps: in the step 2), the chelating agent is glacial acetic acid.
8. The preparation method of the hybrid material based on the photosensitive metal-organic coordination nanocage and the titanium dioxide as claimed in claim 3, wherein the preparation method comprises the following steps: in the step 2), the heating temperature is 50-70 ℃, and the heating time is 20-30 h.
9. The preparation method of the hybrid material based on the photosensitive metal-organic coordination nanocage and the titanium dioxide as claimed in claim 3, wherein the preparation method comprises the following steps: in the step 3), the extraction method is Soxhlet extraction.
10. A photocatalyst comprising a photosensitive metal-organic coordination nanocage and titanium dioxide-based hybrid material of claim 1.
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