CN109331884B - Composite hydrogen production catalyst and preparation method and application thereof - Google Patents
Composite hydrogen production catalyst and preparation method and application thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000001257 hydrogen Substances 0.000 title claims abstract description 63
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 35
- 230000001699 photocatalysis Effects 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 125000002091 cationic group Chemical group 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- 229960005070 ascorbic acid Drugs 0.000 claims description 15
- 235000010323 ascorbic acid Nutrition 0.000 claims description 14
- 239000011668 ascorbic acid Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910052724 xenon Inorganic materials 0.000 claims description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- ZMMJGEGLRURXTF-UHFFFAOYSA-N ethidium bromide Chemical compound [Br-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 ZMMJGEGLRURXTF-UHFFFAOYSA-N 0.000 claims description 6
- 229960005542 ethidium bromide Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000007792 addition Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- -1 ammonium heptamolybdate tetrahydrate Chemical class 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- KAPNIDMXEKQLMQ-UHFFFAOYSA-N 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde Chemical compound OC1=C(C=O)C(O)=C(C=O)C(O)=C1C=O KAPNIDMXEKQLMQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 7
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 5
- 150000001450 anions Chemical class 0.000 abstract description 3
- 238000005341 cation exchange Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000011943 nanocatalyst Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000001144 powder X-ray diffraction data Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
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- 238000004064 recycling Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- MHXLAKJJNRIVDR-UHFFFAOYSA-N 2,4,6-trihydroxybenzene-1,3,5-tricarboxylic acid Chemical compound OC1=C(C(=C(C(=C1C(=O)O)O)C(=O)O)O)C(=O)O MHXLAKJJNRIVDR-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B01J35/39—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a covalent organic framework package based [ Mo ]3S13]2‑A cluster composite hydrogen production catalyst, a preparation method and an application thereof relate to the technical field of nano-catalysts and photocatalysis. The composite catalyst takes a cationic covalent organic framework EB-COF as a carrier, and anions [ Mo ] with high catalytic activity are subjected to anion-cation exchange3S13]2‑The clusters are packaged in a COF framework to obtain the high-efficiency and stable composite catalyst. The hydrogen production rate is as high as 13215μmol h‑1 g‑1The composite catalyst can improve [ Mo ]3S13]2‑The catalytic stability of the clusters is realized, and the conversion from the homogeneous catalyst to the heterogeneous catalyst is realized, and the heterogeneous catalyst can be recycled through centrifugal separation, so that the utilization rate of the catalyst is greatly improved.
Description
Technical Field
The invention relates to the technical field of nano-catalyst and photocatalysis, in particular to a covalent organic framework encapsulation based [ Mo ]3S13]2-A cluster composite hydrogen production catalyst, a preparation method thereof and application thereof in photocatalytic hydrogen production.
Background
With the rapid development of global economy and industry, the decreasing reserves of fossil fuels and the serious environmental pollution problems caused by the heavy use of fossil fuels have stimulated a great research interest of global scientists in clean renewable energy sources. Solar energy is an inexhaustible low-cost energy source, and an effective way for converting the solar energy into chemical energy and effectively storing the chemical energy is provided.
Due to the characteristics of high energy density, no pollution of combustion products, convenience in storage and the like, hydrogen becomes one of new energy sources hopeful to replace fossil energy. The hydrogen production by utilizing solar energy can effectively convert the solar energy into hydrogen energy which can be directly utilized and is beneficial to storage. The first report of utilizing semiconductor TiO in 1972 by Fujishima project group of Japan2The electrode decomposes water to produce hydrogen under the catalysis of ultraviolet light, and the feasibility of converting solar energy to hydrogen energy is disclosed. Therefore, the method has aroused great interest of various scientists in the technology of decomposing hydrogen in water. Water, which is a compound existing in large quantities and stable on earth, hardly achieves self-decomposition and completes conversion to hydrogen gas in a spontaneous state. Whereas the voltage required to decompose water in the cell is only 1.23eV, as calculated by the nernst equation, the thermodynamic feasibility suggests that this energy conversion process can be achieved by finding a suitable catalyst.
Bensenbacher topic group and Min topic group successively reported [ Mo ] with multiple catalytic sites in 2014 and 2018 respectively3S13]2-The clusters have excellent catalytic performance in hydrogen production by electrocatalysis and photocatalytic water decomposition. However, since [ Mo ] is3S13]2-The clusters participate in the reaction in a homogeneous form in the reaction of producing hydrogen by photocatalytic decomposition, and possible self-decomposition exists, so that the clusters cannot be recycled, and the utilization rate of the catalyst is greatly reduced. For this purpose, a homogeneous catalyst [ Mo ] was sought3S13]2-The method of converting clusters into heterogeneous catalysts to recycle them has become one of the research hotspots.
Disclosure of Invention
The invention aims to provide a covalent organic framework encapsulation [ Mo ] based on recycling3S13]2-A cluster high-efficiency composite hydrogen production catalyst; another object is to provide a process for the preparation thereofAnd applications.
In order to realize the purpose of the invention, the invention takes cationic covalent organic framework EB-COF as a carrier, and is stirred with [ Mo ] at normal temperature3S13]2-The nano-scale composite material is obtained by the clusters through anion-cation exchange, the conversion from a homogeneous catalyst to a heterogeneous catalyst is completed, the cyclic recycling of the catalyst is realized, and the nano-scale composite material is used for catalyzing water decomposition to produce hydrogen under the irradiation of visible light.
The preparation method of the high-efficiency visible light catalytic water decomposition hydrogen production catalyst comprises the following steps:
(1) sequentially adding 2,4, 6-trihydroxy-1, 3, 5-benzene tricarboaldehyde, ethidium bromide, 1, 4-dioxane, mesitylene and glacial acetic acid into a heat-resistant glass tube, quickly freezing the tube in a 77K-80K liquid nitrogen bath, degassing through freezing-air extraction-unfreezing circulation, reacting at a constant temperature of 110-120 ℃, and naturally cooling to room temperature to obtain a suspension.
(2) And (3) filtering the suspension obtained in the step (1), washing, drying and grinding to obtain EB-COF solid powder.
(3) Ammonium heptamolybdate tetrahydrate is dissolved in water and the ammonium polysulfide solution is then added. Stirring and reacting at constant temperature of 90-96 ℃. Cooling to room temperature after the reaction is finished, standing for precipitation, filtering the obtained solid, washing, drying and grinding to obtain the [ Mo ]3S13]2-And (3) solid powder.
(4) The obtained [ Mo ]3S13]2-The powder was dissolved in a sodium hydrogencarbonate solution, and the EB-COF powder obtained in (2) was added thereto and the reaction was stirred at room temperature to obtain a suspension.
(5) And (4) centrifuging, carrying out ultrasonic treatment and washing the suspension obtained in the step (4). Drying and grinding to obtain Mo3S13@ EB-COF solid powder.
In the step (1), the molar ratio of the 2,4, 6-trihydroxy-1, 3, 5-benzene triformal to the ethidium bromide is 1-3: 3.
In the step (1), the volume ratio of the 1, 4-dioxane to the mesitylene is 0.5-2: 1.
The molar concentration of the glacial acetic acid added in the step (1) is 5-6 mol/L.
The composite material is used as a catalyst to be applied to a system for decomposing water into hydrogen by visible light, and after the conditions are optimized, the composite material and a proper photosensitizer and a sacrificial agent are used together to complete hydrogen production by decomposing water under the irradiation of the visible light in an N 'N' -dimethylformamide/aqueous solution system. The preferred photosensitizer in the photocatalytic hydrogen production process is ruthenium terpyridyl chloride, the preferred sacrificial agent is ascorbic acid, and the molar concentration of the ascorbic acid in an N 'N' -dimethylformamide/water solution system is preferably 300 mmol/L.
The invention has the advantages that: the composite catalyst takes a cationic covalent organic framework material EB-COF as a carrier, and anions [ Mo ] with high catalytic activity are subjected to anion-cation exchange3S13]2-The clusters are packaged in COF, so that the high-efficiency and stable composite catalyst is obtained. The hydrogen production rate is as high as 13215 mu mol h-1g-1The composite catalyst can improve [ Mo ]3S13]2-The catalytic stability of the clusters is realized, and the conversion from the homogeneous catalyst to the heterogeneous catalyst is realized, and the heterogeneous catalyst can be recycled through centrifugal separation, so that the utilization rate of the catalyst is greatly improved. At the same time improve [ Mo ]3S13]2-Stability of the clusters in photocatalytic water splitting reactions. The catalyst has the advantages of simple synthesis method, high yield and the like. Provides a new way for preparing the novel photocatalytic hydrogen production composite catalyst and also provides a new synthesis idea for converting other homogeneous catalysts into heterogeneous catalysts.
Drawings
FIG. 1 is a comparison of powder X-ray diffraction (PXRD) patterns and simulated calculated PXRD patterns of EB-COF synthesized over a catalyst of the present invention; wherein, 1 is EB-COF synthesized in the invention, and 2 is PXRD result of simulation calculation; it can be seen that the prepared EB-COF has high purity and good crystallinity.
FIG. 2 shows the synthesis of [ Mo ] by the catalyst of the present invention3S13]2-A powder X-ray diffraction (PXRD) pattern of the cluster and a single crystal simulated PXRD pattern contrast plot; wherein 1 is [ Mo ] synthesized by the invention3S13]2-Cluster sample, 2 is the single crystal simulation result; it can be seen that [ Mo ] is produced3S13]2-High cluster purityThe crystallinity is good;
FIG. 3 is a powder X-ray diffraction (PXRD) pattern of a catalyst of the present invention and a powder X-ray diffraction single crystal of EB-COF and a comparison of its simulated PXRD patterns; wherein, 1 is the catalyst of the invention, and 2 is EB-COF synthesized in the invention; the diffraction peak of the catalyst of the invention at 3.6 degrees (100 crystal planes) is sharply weakened due to the filling of the guest molecules to the COF one-dimensional pore channels;
FIG. 4a is a nitrogen adsorption isotherm at 77k for the catalyst of the invention and EB-COF synthesized in the invention, and FIG. 4b is a pore size distribution plot for the catalyst of the invention and EB-COF synthesized in the invention. Wherein, 1 is the catalyst of the invention, and 2 is EB-COF synthesized in the invention. Anion [ Mo ] can be seen3S13]2-Filling one-dimensional pore channels occupying EB-COF;
FIG. 5 is an elemental surface scanning (mapping) electron micrograph of the catalyst of the present invention, which shows that Mo and S elements are present and uniformly distributed in the composite sample, further proving that [ Mo ] is3S13]2-Uniformly compounding in the EB-COF material;
FIG. 6 is a comparison graph of the effect of different organic solvents on hydrogen production during the photocatalytic hydrogen production process of the catalyst of the present invention, from which it can be seen that the optimal solvent system is N 'N' -dimethylformamide and water;
FIG. 7 is a comparison graph of the effect of different volume ratios of N 'N' -dimethylformamide to water on hydrogen production in the photocatalytic hydrogen production process of the catalyst of the present invention, from which it can be seen that the optimal volume ratio of N 'N' -dimethylformamide to water is 1: 1;
FIG. 8 is a comparison graph of the effect of different amounts of the photosensitizer terpyridine ruthenium chloride added on the hydrogen production effect in the photocatalytic hydrogen production process of the catalyst of the present invention, from which it can be seen that the optimal amount of the photosensitizer added is 10 mg;
FIG. 9 is a graph comparing the effect of ascorbic acid as a sacrificial agent with different molar concentrations on hydrogen production in the photocatalytic hydrogen production process of the catalyst of the present invention, from which it can be seen that the optimal molar concentration of the sacrificial agent is 300 mmol/L;
FIG. 10 is a comparison graph of the effect of different catalyst additions on hydrogen production during photocatalytic hydrogen production by using the catalyst of the present invention, from which it can be seen that the optimum catalyst addition is 0.5 mg;
FIG. 11 is a diagram of four groups of circulation hydrogen production effect of the catalyst of the present invention, from which it can be seen that the sample is very stable, and the catalytic performance is basically not attenuated after 4 times of circulation tests.
Detailed Description
The invention is further illustrated by the following examples:
example 1: synthesis of covalent organic framework based encapsulation [ Mo ]3S13]2-Cluster composite hydrogen production catalyst
(1) 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid, ethidium bromide, 1, 4-dioxane, mesitylene and glacial acetic acid are sequentially added into a heat-resistant glass tube, and then the tube is quickly frozen under 77K (liquid nitrogen bath) and degassed through three freezing-air extraction-unfreezing cycles. Reacting at constant temperature of 120 ℃, and naturally cooling to room temperature to obtain suspension. The molar ratio of the 2,4, 6-trihydroxy-1, 3, 5-benzene triformal to the ethidium bromide is 2: 3; the volume ratio of the 1, 4-dioxane to the mesitylene is 1: 1; the molar concentration of the glacial acetic acid added is 6 mol/L.
(2) The suspension obtained in (1) was filtered and washed three times with tetrahydrofuran to obtain a dark red solid. And (3) carrying out solvent exchange on the dark red solid in tetrahydrofuran and methanol, then carrying out vacuum drying for 12 hours at the temperature of 100 ℃, taking out and grinding to obtain dark red solid powder, namely EB-COF used for preparing the catalyst.
(3) Ammonium heptamolybdate tetrahydrate is dissolved in water and the ammonium polysulfide solution is then added. The reaction was stirred at constant temperature at 96 ℃ for 5 hours. Cooled to room temperature and settled to give a dark red solid. The solid was filtered and then washed three times each with water and ethanol. Dispersing the washed dark red solid in toluene, heating, refluxing and stirring at 80 ℃ for 3 hours, standing, removing the upper solution while the solution is hot, and repeating the steps for 3 to 4 times; then filtering the solid, drying in the air, grinding to obtain orange red solid powder, namely [ Mo ] used for preparing the catalyst3S13]2-And (4) clustering.
(4) The [ Mo ] obtained in (3)3S13]2-The powder (150mg) was dissolved in a sodium hydrogencarbonate solution (250mL) at a molar concentration of 0.05mol/L to give an orange-red solution, and the EB-COF powder (100mg) obtained in (2) was dispersed in the orange-red solution and stirred at room temperature for 24 hours to give a dark-red suspension. Centrifuging the suspension, washing with water for multiple times with ultrasound until the solution is colorless, vacuum drying at 100 deg.C for 12 hr, taking out, and grinding to obtain dark red solid powder as catalyst Mo3S13@ EB-COF solid powder.
Application example 1:
2mg of the composite catalyst prepared in example 1 and 10mg of ruthenium terpyridine chloride are added into a photocatalytic reactor, different organic solvents (the volume ratio of the organic solvent to water is 1:1, v/v) and ascorbic acid with the molar concentration of 50mmol/L are selected for photocatalytic hydrogen production under the irradiation of 300W visible light (a 420nm filter is added) of a xenon lamp, the hydrogen production amount of the different organic solvents is shown in the graph of FIG. 6, and the most preferable organic solvent is N 'N' dimethylformamide.
Application example 2:
2mg of the composite catalyst prepared in example 1 and 10mg of ruthenium terpyridyl chloride are added into a photocatalytic reactor, different volume ratios of N ', N' -dimethylformamide to water and ascorbic acid with the molar concentration of 50mmol/L are selected for photocatalytic hydrogen production under the irradiation of 300W visible light (a 420nm filter is added) of a xenon lamp, and the hydrogen production yield ratio of the N ', N' -dimethylformamide to water with different volume ratios is shown in figure 7, and the most preferable solvent volume ratio is 1: 1.
Application example 3:
under the condition that the volume ratio of N ', N' -dimethylformamide to water is 1:1, 2mg of the composite catalyst prepared in the example 1 and ascorbic acid with the molar concentration of 50mmol/L are added into a photocatalytic reactor, ruthenium terpyridine chloride with different adding amounts is selected, and photocatalytic hydrogen production is carried out under the irradiation of 300W visible light (a 420nm filter is added) of a xenon lamp, wherein the hydrogen production amount of the ruthenium terpyridine chloride with different amounts is shown in a graph 8, and the most preferable adding amount of the ruthenium terpyridine chloride is 10 mg.
Application example 4:
under the condition that the volume ratio of N ', N' -dimethylformamide to water is 1:1, 2mg of the composite catalyst prepared in the example 1 and 10mg of ruthenium terpyridyl chloride are added into a photocatalytic reactor, ascorbic acid with different molar concentrations is selected and subjected to photocatalytic hydrogen production under the irradiation of 300W visible light (a 420nm filter is added) of a xenon lamp, the hydrogen production amount of the ascorbic acid with different molar concentrations is shown in the graph of FIG. 9, and the most preferable molar concentration of the ascorbic acid is 300 mmol/L.
Application example 5:
under the condition that the volume ratio of N ', N' -dimethylformamide to water is 1:1, 10mg of ruthenium terpyridine chloride and ascorbic acid with the molar concentration of 300mmol/L are added into a photocatalytic reactor, the composite catalyst prepared in the example 1 with different adding amounts is selected, and photocatalytic hydrogen production is carried out under the irradiation of 300W visible light (with a 420nm filter) of a xenon lamp, and the hydrogen production amount of the composite catalyst prepared in the example 1 with different adding amounts is 0.5mg, as shown in the graph 10, and the most preferable adding amount of the composite catalyst prepared in the example 1 is 0.5 mg.
Application example 6:
after optimizing the hydrogen production conditions, 0.5mg of the composite catalyst prepared in example 1 is poured into a photocatalytic reactor, 10mg of ruthenium terpyridine chloride is added, 15mL of an N 'N' -dimethylformamide/water (1:1, v/v) solution with the molar concentration of 300mmol/L ascorbic acid is injected, nitrogen is introduced for 30 minutes to replace the air in the system so as to ensure an oxygen-free environment, a xenon lamp is used for irradiating with 300W visible light (with a 420nm optical filter), and the distance between a light source and the reactor is 10 cm. Detecting by an Agilent 7820A gas chromatography, continuously reacting for 18 hours under illumination, manually feeding a sample once every one hour for detection, and ensuring that the hydrogen peak area tends to be stable after 18 hours. The hydrogen production rate is as high as 13215 mu mol h-1g-1。
Application example 7:
6mg of the composite catalyst prepared in example 1 and 10mg of ruthenium terpyridine chloride were charged into a photocatalytic reactor, and 15mL of a solution of ascorbic acid in N 'N' -dimethylformamide/water (1:1, v/v) at a molar concentration of 300mmol/L was further injected. Performing a first group of photocatalytic hydrogen production under the irradiation of a xenon lamp 300W visible light (420nm filter), measuring the hydrogen production by using gas chromatography, recovering the catalyst after centrifugal separation after 5 hours of illumination, washing the centrifugally recovered sample with deionized water, drying, grinding and recovering. Then 10mg of ruthenium terpyridine chloride and 15mL of a solution of ascorbic acid in N 'N' -dimethylformamide/water (1:1, v/v) in a molar concentration of 300mmol/L were added again. And measuring the photocatalytic hydrogen production of the second group, and comparing the hydrogen production of the fourth group with that of the second group in the same way to obtain a four-group circular hydrogen production effect diagram of the catalyst shown in the figure 11. As shown in FIG. 11, the four groups of circulating hydrogen production did not decrease significantly, indicating that the catalyst has good recycling effect and high recyclability.
Claims (3)
1. The composite hydrogen production catalyst is characterized in that the composite hydrogen production catalyst takes cationic covalent organic framework EB-COF as a carrier and [ Mo [ -COF [ -Mo [ ]3S13]2-Clustering to obtain a nano-scale composite material in an ion exchange mode; the composite hydrogen production catalyst is prepared by the following method:
(1) sequentially adding 2,4, 6-trihydroxy-1, 3, 5-benzene tricarboaldehyde, ethidium bromide, 1, 4-dioxane, mesitylene and glacial acetic acid into a heat-resistant glass tube, quickly freezing the tube in a 77K-88K liquid nitrogen bath, degassing through freezing-air extraction-unfreezing circulation, reacting at a constant temperature of 110-120 ℃, and reducing the natural condition to room temperature to obtain a suspension; wherein the molar ratio of the 2,4, 6-trihydroxy-1, 3, 5-benzene triformal to the ethidium bromide is 1-3: 3; the volume ratio of the 1, 4-dioxane to the mesitylene is 0.5-2: 1; adding glacial acetic acid with the molar concentration of 5-6 mol/L;
(2) filtering the suspension obtained in the step (1), washing, drying and grinding to obtain EB-COF solid powder;
(3) dissolving ammonium heptamolybdate tetrahydrate in water, then adding an ammonium polysulfide solution, and stirring at a constant temperature of 90-96 ℃ for reaction; cooling to room temperature after the reaction is finished, standing for precipitation, filtering the obtained solid, washing, drying and grinding to obtain the [ Mo ]3S13]2-A solid powder;
(4) will obtain [ Mo3S13]2-Dissolving the powder in a sodium bicarbonate solution, adding the EB-COF powder obtained in the step (2), and stirring for reaction at room temperature to obtain a suspension; centrifuging the suspension, performing ultrasonic treatment, washing, drying and grinding to obtain Mo3S13@ EB-COF solid powder.
2. The application of the composite hydrogen production catalyst in photocatalytic hydrogen production as claimed in claim 1, characterized in that in the photocatalytic reactor, the composite hydrogen production catalyst and ruthenium terpyridine chloride are added into N 'N' -dimethylformamide/water solution of ascorbic acid, and photocatalytic hydrogen production is performed under the irradiation of 300W visible light from a xenon lamp.
3. The application of the composite hydrogen production catalyst in photocatalytic hydrogen production as claimed in claim 2, wherein the volume ratio of N 'N' -dimethyl formamide to water solution is 1:1, the addition amount of terpyridine ruthenium chloride is 10mg, the molar concentration of ascorbic acid in the N 'N' -dimethyl formamide to water solution system is 300mmol/L, and the addition amount of the composite hydrogen production catalyst is 0.5 mg.
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