CN114249774A - Organic cobalt complex and preparation method thereof - Google Patents
Organic cobalt complex and preparation method thereof Download PDFInfo
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- CN114249774A CN114249774A CN202210023289.3A CN202210023289A CN114249774A CN 114249774 A CN114249774 A CN 114249774A CN 202210023289 A CN202210023289 A CN 202210023289A CN 114249774 A CN114249774 A CN 114249774A
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- 150000004700 cobalt complex Chemical class 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000013110 organic ligand Substances 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 23
- 239000010941 cobalt Substances 0.000 claims abstract description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 239000011941 photocatalyst Substances 0.000 description 14
- 229910002915 BiVO4 Inorganic materials 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 229910019897 RuOx Inorganic materials 0.000 description 6
- 229910002370 SrTiO3 Inorganic materials 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
-
- 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
-
- 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
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
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Abstract
The invention provides an organic cobalt complex and a preparation method thereof, relating to the technical field of chemical synthesis and comprising the following steps: the organic ligand cobalt complex is as follows: dissolving a divalent cobalt source and an organic ligand I into an aqueous solution together, and stirring at 40-80 ℃ until no obvious solid particles exist; wherein the feeding molar ratio of the cobalt source to the organic ligand I is 1: 10-10: 1, and the concentration of the cobalt source is 0.01M-100M; adding a proper amount of hydrogen peroxide at a certain temperature under the condition of stirring; the concentration of hydrogen peroxide is more than 0.1 percent; continuously stirring, and adding a proper amount of inorganic acid at a certain temperature; wherein the temperature is 0-80 ℃, and the concentration of the inorganic acid is more than 0.1M; heating in water bath or oil bath while stirring until the solution is almost evaporated to dryness; adding a certain amount of organic solvent, stirring, separating crystal particles, and washing with the organic solvent for more than 1 time; and drying the obtained solid sample to obtain the organic ligand I coordination cobalt complex. The ionic couple can be used as a charge transport carrier for hydrogen production by photocatalytic water decomposition.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, and particularly relates to an organic cobalt complex and a preparation method thereof.
Background
In the prior art, the cobalt complex is usually synthesized by adding inorganic acid, hydrochloric acid and the like in Chinese patent CN108997774A, or by solid-phase synthesis in Chinese patent CN101767037A, which improves the quality of the final product and improves the catalytic effect.
However, the above methods do not form research on application of electricity to energy storage to electrocatalysis, and few references are made to technologies from electricity to energy storage to catalysis, electrochemical energy storage per se can achieve the effect of water splitting and metering in catalysis, and meanwhile, the stability and the cyclicity of finished products can be further improved.
Disclosure of Invention
In view of the above, the present invention provides an organic cobalt complex and a preparation method thereof, which can make an ionic couple thereof serve as a charge transport carrier for hydrogen production through photocatalytic water splitting.
The invention provides an organic cobalt complex and a preparation method thereof, and the preparation method specifically comprises the following steps: the organic ligand cobalt complex is as follows:
s1, dissolving a divalent cobalt source and an organic ligand I into an aqueous solution together, and stirring at 40-80 ℃ until no obvious solid particles exist; wherein the feeding molar ratio of the cobalt source to the organic ligand I is 1: 10-10: 1, and the concentration of the cobalt source is 0.01M-100M;
s2, adding a proper amount of hydrogen peroxide at a certain temperature under the stirring condition; wherein the temperature is 0-80 ℃, and the concentration of hydrogen peroxide is more than 0.1%;
s3, continuously stirring, and adding a proper amount of inorganic acid at a certain temperature; wherein the temperature is 0-80 ℃, and the concentration of the inorganic acid is more than 0.1M;
s4, under the stirring condition, placing the mixture in a water bath or an oil bath to be heated until the solution is almost evaporated to be dry; wherein the heating temperature is 50-220 ℃;
s5, adding a certain amount of organic solvent, stirring, separating crystal particles, and washing for more than 1 time by using the organic solvent; wherein the separation mode comprises one or more than two solid-liquid separation methods of filtration, suction filtration, centrifugation and the like;
and S6, drying the obtained solid sample to obtain the organic ligand I coordination cobalt complex.
Optionally, the further organic ligand synthesis of the organic ligand i coordination cobalt complex comprises the following specific steps:
A. dissolving a certain amount of organic ligand I coordination cobalt complex in secondary water at the temperature of 40-80 ℃, and stirring until the organic ligand I coordination cobalt complex is dissolved; wherein the concentration of the organic ligand I coordination cobalt complex is 0.01M-100M; the temperature of the secondary water is 0-100 ℃;
B. continuously adding a certain amount of organic ligand I; wherein the concentration of the organic ligand I is 0.01M-100M;
C. stirring until the solution is subjected to color conversion, heating the solution to a certain temperature, and stopping heating when crystals are separated out from the solution; wherein the heating temperature is 60-150 ℃;
D. adding a certain amount of organic solvent, stirring, separating crystal particles, and washing with the organic solvent for more than 1 time; wherein the separation mode comprises one or more than two solid-liquid separation methods of filtration, suction filtration, centrifugation and the like; the adding amount of acetone is 1-200 mL;
E. and drying the obtained solid sample to obtain the organic ligand II coordination cobalt complex.
Optionally, the drying temperature is 0-150 ℃, and the drying time is more than 1 h.
Optionally, the cobalt source used in the synthesis of the bipyridyl coordinated cobalt complex comprises one or more of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt perchlorate; the adopted inorganic acid comprises one or more than two of carbonic acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid and hexafluorophosphoric acid; the organic solvent includes one or more of ethanol, acetone and isopropanol.
Advantageous effects
1. The invention prepares the bipyridyl coordinated cobalt complex with lower oxidation-reduction potential by a simple liquid phase synthesis method, and the oxidation-reduction potential of the bipyridyl coordinated cobalt complex is 0.12Vvsag | AgCl | KCl. The complex can be used as a charge transport carrier to achieve complete water splitting by the Z mechanism.
2. Compared with other methods, the preparation method provided by the invention is simple to operate and easy to amplify and synthesize, and compared with the prior art, the soluble redox couple applied to the Z mechanism has better stability, has larger molecular volume compared with the soluble redox couple applied to the Z mechanism, can realize effective isolation application, and provides support for step-by-step production of hydrogen and oxygen.
3. The invention provides an organic ligand coordinated cobalt complex and an ionic pair thereof, which can be used as charge transmission carriers for hydrogen production by photocatalytic water splitting. Meanwhile, the complex ion pair has good stability and cyclicity. The preparation method is simple, has good repeatability, is easy for large-scale production and preparation, and can also be applied to electrocatalysis.
4: the invention uses specific temperature reaction and simple flow, after combining organic ligand and other substances to mix, the invention can achieve the promotion of electrochemical energy storage on the catalytic flow and the improvement of the synthesis rate under the finished product, so that the reduction potential of the product can reach a high-quality value.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
The drawings in the following description relate to some embodiments of the invention only and are not intended to limit the invention.
In the drawings:
FIG. 1 is a mass spectrum of the synthesized bipyridyl-complexed cobalt complex molecule.
FIG. 2 is a cyclic voltammetry test plot of the synthetically prepared bipyridyl-complexed cobalt complex molecules.
FIG. 3 is a diagram showing the results of a complete water splitting test performed with BiVO4 as an oxygen-producing photocatalyst, SrTiO3: Ru as a hydrogen-producing photocatalyst, and a bipyridine complex as a charge transport carrier.
FIG. 4 shows the performance test results of BiVO4, WO3 and SrTiO3 as oxygen-generating photocatalysts and bipyridyl coordination cobalt complex as an energy storage couple.
FIG. 5 shows the performance test results of the cobalt bipyridyl complex under the conditions that BiVO4 photocatalyst supports different promoters.
FIG. 6 shows the performance test results of the bipyridyl complex under the condition of BiVO4 photocatalyst supported double-promoter.
FIG. 7 is a graph of the oxygen evolution time of a cobalt bipyridyl complex on a BiVO4 photocatalyst using Pt and RuOx as dual promoters.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows: please refer to fig. 1 to 7:
the invention provides an organic cobalt complex and a preparation method thereof, comprising the following steps: the organic ligand cobalt complex is as follows:
s1, dissolving a divalent cobalt source and an organic ligand I into an aqueous solution together, and stirring at 40-80 ℃ until no obvious solid particles exist; wherein the feeding molar ratio of the cobalt source to the organic ligand I is 1: 10-10: 1, and the concentration of the cobalt source is 0.01M-100M;
s2, adding a proper amount of hydrogen peroxide at a certain temperature under the stirring condition; wherein the temperature is 0-80 ℃, and the concentration of hydrogen peroxide is more than 0.1%;
s3, continuously stirring, and adding a proper amount of inorganic acid at a certain temperature; wherein the temperature is 0-80 ℃, and the concentration of the inorganic acid is more than 0.1M;
s4, under the stirring condition, placing the mixture in a water bath or an oil bath to be heated until the solution is almost evaporated to be dry; wherein the heating temperature is 50-220 ℃;
s5, adding a certain amount of organic solvent, stirring, separating crystal particles, and washing for more than 1 time by using the organic solvent; wherein the separation mode comprises one or more than two solid-liquid separation methods of filtration, suction filtration, centrifugation and the like;
and S6, drying the obtained solid sample to obtain the organic ligand I coordination cobalt complex.
Further, the organic ligand I coordinates the further organic ligand synthesis of the cobalt complex, the steps are as follows:
A. dissolving a certain amount of organic ligand I coordination cobalt complex in secondary water at the temperature of 40-80 ℃, and stirring until the organic ligand I coordination cobalt complex is dissolved; wherein the concentration of the organic ligand I coordination cobalt complex is 0.01M-100M; the temperature of the secondary water is 0-100 ℃;
B. continuously adding a certain amount of organic ligand I; wherein the concentration of the organic ligand I is 0.01M-100M;
C. stirring until the solution is subjected to color conversion, heating the solution to a certain temperature, and stopping heating when crystals are separated out from the solution; wherein the heating temperature is 60-150 ℃;
D. adding a certain amount of organic solvent, stirring, separating crystal particles, and washing with the organic solvent for more than 1 time; wherein the separation mode comprises one or more than two solid-liquid separation methods of filtration, suction filtration, centrifugation and the like; the adding amount of acetone is 1-200 mL;
E. and drying the obtained solid sample to obtain the organic ligand II coordination cobalt complex.
Furthermore, the drying temperature is 0-150 ℃, and the drying time is more than 1 h.
Further, the cobalt source adopted in the synthesis of the cobalt complex coordinated by the bipyridine comprises one or more than two of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt perchlorate; the adopted inorganic acid comprises one or more than two of carbonic acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid and hexafluorophosphoric acid; the organic solvent includes one or more of ethanol, acetone and isopropanol.
The prepared cobalt complex can be used as a charge transmission carrier in the photocatalytic reaction process, can realize complete water decomposition and hydrogen production after being coupled with the hydrogen production end and the oxygen production end photocatalyst, and in addition, the overpotential required in the electrochemical hydrogen discharge process is lower; the cobalt complex of the organic ligand is applied to the hydrogen production by photocatalytic water decomposition and the electrochemical hydrogen discharge reaction in the low valence state; the cobalt complex prepared from the cobalt complex of the organic ligand can be used as a charge transmission carrier in the electrocatalytic reaction process, and is applied to the electrochemical hydrogen discharge reaction during electrocatalytic water decomposition hydrogen production and low-valence state.
Wherein, the solution method is used for preparing the cobalt complex of bipyridyl complex:
adding 10mmol of cobalt chloride hexahydrate, 20mmol of bipyridine and 10mL of bipyridine into a 100mL round-bottom flask, and stirring at 40 ℃ until no solid particles are obvious;
under stirring, 20mL of 10% hydrogen peroxide was added at room temperature. Continuously stirring uniformly, adding 2.5mL of concentrated hydrochloric acid, and stirring for 30 minutes at 40 ℃;
under the condition of stirring, placing the mixture in an oil bath pot, heating and refluxing until the solution is almost evaporated to dryness, wherein the reaction temperature is 140 ℃;
adding 50mL of hot ethanol into the flask, stirring at 80 ℃ to disperse crystal particles, performing suction filtration, and washing with hot ethanol for 3 times;
the resulting crystals were dried overnight at room temperature.
The obtained bipyridyl coordination cobalt complex crystal is a pure-phase trivalent bipyridyl dichloro complex cobalt complex doped with a small amount of monomers, the oxidation-reduction potential of the pure-phase trivalent bipyridyl dichloro complex cobalt complex crystal is about 0.12Vvs. Ag (silver) AgCl (potassium chloride) KCl, and the result is shown in figures 1 and 2, and the synthesized bipyridyl dichloro complex and terpyridyl complex cobalt complex is a pure-phase trivalent cobalt complex molecular structure as can be seen from figure 1; it can be seen from FIG. 2 that the redox potentials of the synthesized cobalt complexes of bipyridine coordination and terpyridine coordination are both around 0.12Vvs.
Performance testing for cobalt complex formation of bipyridine complexes under experiment:
the performance test of Z mechanism complete decomposition water property by using the bipyridine complex cobalt complex as a charge transport carrier:
0.5mM of cobalt bipyridine complex is added into 150mL of secondary water, and then 0.1gRu/SrTiO3 of Rh and 0.2gPt-BiVO4 of hydrogen-producing and oxygen-producing photocatalyst are added. A300W xenon lamp is used for irradiation, the gas chromatography is used for detecting hydrogen and oxygen, the hydrogen and oxygen are produced in a metering ratio, the test result is shown in figure 3, and the system successfully realizes the complete decomposition of water under the illumination condition to produce the hydrogen and oxygen in the metering ratio.
The photocatalytic oxygen generation performance of the bipyridine complex in different photocatalyst systems is tested as follows:
after 3.75mM of cobalt bipyridine complex was added to 100mL of secondary water, 0.1g of different oxygen-generating photocatalysts (including BiVO4, WO3, SrTiO3 and the like) were added, and the photocatalytic oxygen-generating activity was detected by gas chromatography under the irradiation of a 300W xenon lamp light source, as shown in FIG. 4, it can be seen that BiVO4 has higher performance than WO3 and SrTiO 3. The performance of the cobalt complex coordination compound is higher than that of the cobalt complex coordination compound.
The curve test of the photocatalytic oxygen generation reaction time of the bipyridyl complex in a Pt/RuOx/BiVO4 photocatalyst system:
6.2mM of cobalt bipyridine complex was added to 100mL of secondary water followed by 0.1gPt/RuOx/BiVO4 photocatalyst. The reaction time curve was tested under 300W xenon lamp illumination, and the test results are shown in FIG. 5, from which it can be seen that Pt, Au, MnOx, RuOx exhibit good performance as reduction and oxidation promoters, respectively.
The apparent quantum efficiency of oxygen generation of the bipyridyl complex in a Pt/RuOx/BiVO4 photocatalyst system is as follows:
after 2.5mM of cobalt bipyridine complex is added into 100mL of secondary water, 0.2gPt/RuOx/BiVO4 photocatalyst is added, a 300W xenon lamp is used as a light source, monochromatic light filters with different wavelengths are arranged, the reactor is in an upper illumination type, an apparent quantum efficiency test is carried out, the test result is shown in figure 6, and the photocatalytic reaction performance of the system can be further improved by loading the double promoters.
The quantum efficiency is calculated by the formula:
Ф(％)＝(AR/I)×100％
where Φ is the apparent quantum efficiency, A is the correction factor (H2 is 2, O2 is 4), R is the rate at which the gas is produced, and I is the total number of photons.
According to the apparent quantum efficiency test method, the apparent quantum efficiency of the catalyst at 420nm is measured to reach more than 24%.
And (3) testing the electrochemical stability of the bipyridine complex cobalt complex:
the test result is shown in figure 7, and it can be seen from the figure that the oxygen yield can reach the theoretical value along with the reaction, which indicates that the bipyridyl complex is completely converted in the reaction, and the reverse reaction does not exist in the reaction process.
Example two:
solution method preparation of terpyridine complexed cobalt complex:
dissolving 39mmol of cobalt bipyridine complex in 10mL of secondary water at 80 ℃, and stirring until the cobalt bipyridine complex is completely dissolved;
and continuously adding 8mmol of bipyridyl, stirring until the solution turns from purple red to yellow, heating the solution to 90 ℃, and stopping heating when crystals are separated out from the solution.
Adding 15mL of acetone, stirring, performing suction filtration separation, and washing with acetone for 3 times;
the resulting solid sample was dried overnight at room temperature.
The obtained bipyridyl complex crystal is a pure phase trivalent terpyridine complex cobalt complex doped with a small amount of monomer, and the oxidation-reduction potential of the complex cobalt complex is about 0.12Vvs. Ag/AgCl/KCl, and the results are shown in FIG. 1 and FIG. 2.
The difference between this example and the first example is that as shown in fig. 1 and 2, the further synthesized cobalt complex has the advantages of more stable relative strength, less fluctuation of electrical energy properties, and the like.
The above description is intended to be illustrative of the present invention and not to limit the scope of the invention, which is defined by the claims appended hereto.
Claims (4)
1. The preparation method of the organic cobalt complex is characterized in that the cobalt complex containing the organic ligand is as follows:
s1, dissolving a divalent cobalt source and an organic ligand I into an aqueous solution together, and stirring at 40-80 ℃ until no obvious solid particles exist; wherein the feeding molar ratio of the cobalt source to the organic ligand I is 1: 10-10: 1, and the concentration of the cobalt source is 0.01M-100M;
s2, adding a proper amount of hydrogen peroxide at a certain temperature under the stirring condition; wherein the temperature is 0-80 ℃, and the concentration of hydrogen peroxide is more than 0.1%;
s3, continuously stirring, and adding a proper amount of inorganic acid at a certain temperature; wherein the temperature is 0-80 ℃, and the concentration of the inorganic acid is more than 0.1M;
s4, under the stirring condition, placing the mixture in a water bath or an oil bath to be heated until the solution is almost evaporated to be dry; wherein the heating temperature is 50-220 ℃;
s5, adding a certain amount of organic solvent, stirring, separating crystal particles, and washing for more than 1 time by using the organic solvent; wherein the separation mode comprises one or more than two solid-liquid separation methods of filtration, suction filtration, centrifugation and the like;
and S6, drying the obtained solid sample to obtain the organic ligand I coordination cobalt complex.
2. The method for preparing organic cobalt complex as claimed in claim 1, wherein the further organic ligand synthesis of organic ligand I coordination cobalt complex comprises the following steps:
A. dissolving a certain amount of organic ligand I coordination cobalt complex in secondary water at the temperature of 40-80 ℃, and stirring until the organic ligand I coordination cobalt complex is dissolved; wherein the concentration of the organic ligand I coordination cobalt complex is 0.01M-100M; the temperature of the secondary water is 0-100 ℃;
B. continuously adding a certain amount of organic ligand I; wherein the concentration of the organic ligand I is 0.01M-100M;
C. stirring until the solution is subjected to color conversion, heating the solution to a certain temperature, and stopping heating when crystals are separated out from the solution; wherein the heating temperature is 60-150 ℃;
D. adding a certain amount of organic solvent, stirring, separating crystal particles, and washing with the organic solvent for more than 1 time; wherein the separation mode comprises one or more than two solid-liquid separation methods of filtration, suction filtration, centrifugation and the like; the adding amount of acetone is 1-200 mL;
E. and drying the obtained solid sample to obtain the organic ligand II coordination cobalt complex.
3. The method for preparing an organic cobalt complex according to claim 1 or 2, wherein the drying temperature is 0 to 150 ℃ and the drying time is 1 hour or more.
4. The organic cobalt complex and the preparation method thereof according to claim 3, wherein the cobalt source used in the synthesis of the bipyridyl coordinated cobalt complex comprises one or more of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt perchlorate; the adopted inorganic acid comprises one or more than two of carbonic acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid and hexafluorophosphoric acid; the organic solvent includes one or more of ethanol, acetone and isopropanol.
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Non-Patent Citations (4)
| Title |
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| ABUZAR TAHERI ET AL.: "Application of a water-soluble cobalt redox couple in free-standing cellulose films for thermal energy harvesting", 《ELECTROCHIMICA ACTA》 * |
| ANTONIN A. VLCEK: "Preparation of Co(dipy)2X2+ complexes (X- = chloride, bromide, iodide, nitrite) by controlled oxidative processes", 《INORGANIC CHEMISTRY》 * |
| GIULIANA GRASSINI-STRAZZ ET AL.: "Preparation and Characterization of Cobalt(III)Bipyridine and Phenanthroline Complexes", 《INORGANICA CHIMICA ACTA》 * |
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