CN110563772B - Nickel mononuclear hydrogenase model substance and intermediate product, preparation method and application thereof - Google Patents
Nickel mononuclear hydrogenase model substance and intermediate product, preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 304
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 156
- 108010020056 Hydrogenase Proteins 0.000 title claims abstract description 77
- 239000000126 substance Substances 0.000 title claims abstract description 56
- 239000013067 intermediate product Substances 0.000 title claims description 39
- 238000002360 preparation method Methods 0.000 title description 8
- 239000003446 ligand Substances 0.000 claims abstract description 31
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000002815 nickel Chemical group 0.000 claims abstract description 19
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000002091 cationic group Chemical group 0.000 claims abstract description 12
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- MHTSJSRDFXZFHQ-UHFFFAOYSA-N quinoline-8-thiol Chemical compound C1=CN=C2C(S)=CC=CC2=C1 MHTSJSRDFXZFHQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000008040 ionic compounds Chemical class 0.000 claims abstract description 4
- -1 tetrafluoroborate anion Chemical class 0.000 claims abstract description 4
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000000460 chlorine Substances 0.000 claims description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- CMDHQKZXDFOKNB-UHFFFAOYSA-N quinoline-8-thiol;sodium Chemical compound [Na].C1=CN=C2C(S)=CC=CC2=C1 CMDHQKZXDFOKNB-UHFFFAOYSA-N 0.000 claims description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 21
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 108090000790 Enzymes Proteins 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 230000003278 mimic effect Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BBHJTCADCKZYSO-UHFFFAOYSA-N 4-(4-ethylcyclohexyl)benzonitrile Chemical compound C1CC(CC)CCC1C1=CC=C(C#N)C=C1 BBHJTCADCKZYSO-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910019785 NBF4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
-
- 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 System
- C07F15/04—Nickel compounds
- C07F15/045—Nickel 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
- 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
- B01J2531/847—Nickel
-
- 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
Abstract
The invention discloses a nickel mononuclear hydrogenase model substance, which has the following chemical structural formula:
wherein, the nickel mononuclear hydrogenase model compound is an ionic compound, a nickel atom is used as the center of a structural unit, and the nickel atom is respectively connected with a diphosphine ligand and a bidentate nitrogen-sulfur ligand [ NS ]]The cationic complex is formed together, the cationic complex has a positive charge, and the cationic complex resists a tetrafluoroborate anion; the diphosphine ligand is 1, 2-bis (diphenylphosphinoethane), and the bidentate nitrogen-sulfur ligand [ NS ]]Is 8-quinoline thiol. The nickel mononuclear hydrogenase model substance has catalytic activity, is a good enzyme-simulated model catalyst, has a stable crystal structure, adopts cheap metal nickel, can reduce the cost and has economical efficiency.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a nickel mononuclear hydrogenase model substance, an intermediate product, a preparation method and application thereof.
Background
With the increase of population, the increase of environmental pollution and the reduction of ore energy, the development of clean energy to replace the traditional energy becomes a great trend. Among these clean energy sources, hydrogen gas, with its high heat of combustion, is free of pollution after combustion, releasing only H2O, renewable and the like, and is widely concerned.
At present in the industryMost of hydrogen production methods are electrolytic water and fossil energy gasification, the hydrogen production technology of the electrolytic water has the defects of large energy consumption and high electric quantity requirement, and the hydrogen production scale is small due to the limitation of an electrolytic device and does not reach the level of energy requirement. The hydrogen production technology of ore energy gasification comprises the steps of firstly, non-regeneration of ore energy and CO generated after reaction2And the like.
In order to find a clean, cheap and efficient method for producing hydrogen, scientists find that certain catalyst exists in organisms
Enzymes that react reversibly, named hydrogenases; hydrogenases mainly include three classes: a plurality of enzyme imitation models are simulated and synthesized by scientists according to the structure and the property of hydrogenase, but most of the enzyme imitation models do not have catalytic activity, and a few of the enzyme imitation models have active complexes, so that the structure is unstable, and the development of hydrogen production by biological enzyme imitation is hindered.
Disclosure of Invention
In view of the above, the present invention aims to provide a nickel mononuclear hydrogenase model, an intermediate thereof, a preparation method and an application thereof, so as to solve the technical problems that most of the mimic enzyme models in the prior art have no catalytic activity, and few of the mimic enzyme models have active complexes, and the structures of the complexes are unstable, which hinder the development of bio-mimic enzyme hydrogen production.
In order to achieve the above object, the present invention provides a nickel mononuclear hydrogenase model, wherein the chemical structural formula of the nickel mononuclear hydrogenase model is as follows:
wherein, the nickel mononuclear hydrogenase model is an ionic compound, a nickel atom is taken as the center of a structural unit, a diphosphine ligand and a bidentate nitrogen-sulfur ligand [ NS ] are respectively connected to the nickel atom to jointly form a cationic complex, the cationic complex has a positive charge, and the cationic complex counter-balances a tetrafluoroborate anion; the diphosphine ligand is 1, 2-bis (diphenylphosphinoethane), and the bidentate nitrogen-sulfur ligand [ NS ] is 8-quinoline thiol.
The second aspect of the invention provides a nickel mononuclear intermediate product, wherein the chemical structural formula of the nickel mononuclear intermediate product is as follows:
wherein, the nickel mononuclear intermediate product takes a nickel atom as the center of a structural unit, the nickel atom is respectively connected with a diphosphine ligand and a bidentate nitrogen-sulfur ligand [ NS ], and the nickel atom is connected with a chlorine atom in a metal bond form; the diphosphine ligand is 1, 2-bis (diphenylphosphinoethane), and the bidentate nitrogen-sulfur ligand [ NS ] is 8-quinoline thiol.
The third aspect of the invention provides a preparation method of a nickel mononuclear intermediate product, which comprises the following steps:
under room temperature, adding Ni (dppe) Cl2Dissolving in a first organic solvent to obtain Ni (dppe) Cl2A solution; dissolving 8-quinolinethiol sodium in a first organic solvent to obtain a 8-quinolinethiol sodium solution;
(iii) dropwise adding the sodium 8-quinolinethiol solution to the Ni (dppe) Cl2In the solution, removing sodium chloride generated in the reaction process, and concentrating under reduced pressure to obtain a nickel mononuclear intermediate product; wherein the sodium 8-quinolinethiol and the Ni (dppe) Cl2The ratio of the amounts of substances (1): 0.8 to 1.3.
Preferably, said sodium 8-quinolinethiol and said Ni (dppe) Cl2The ratio of the amounts of substances (1): 1. preferably, the first organic solvent is dichloromethane or tetrahydrofuran.
The fourth aspect of the invention provides a preparation method of a nickel mononuclear hydrogenase model substance, which comprises the following steps:
under the protection of nitrogen and light, adding the nickel mononuclear intermediate into a second organic solvent for dissolving at room temperature, and adding AgBF4Mixed and dissolved and then subjected to a reverse reactionThe preparation method comprises the following steps of; after the reaction, removing AgCl generated in the reaction process, and removing the second organic solvent by decompression concentration to obtain a nickel mononuclear hydrogenase model substance; wherein the nickel mononuclear intermediate and the AgBF4The ratio of the amounts of substances (1): 0.8 to 1.3.
Preferably, said nickel mononuclear intermediate and said AgBF4The ratio of the amounts of substances (1): 1.
preferably, the second organic solvent is anhydrous acetonitrile or anhydrous acetone.
The fifth aspect of the invention provides the application of the nickel mononuclear hydrogenase model substance in electrocatalysis of protonic acid reduction to hydrogen.
Compared with the prior art, the invention has the following beneficial effects:
the nickel mononuclear hydrogenase model substance provided by the embodiment of the invention has catalytic activity and is a good enzyme simulation model catalyst. Wherein the center of the nickel atom is four-coordinate and presents a plane configuration. The crystal structure of the nickel mononuclear hydrogenase model substance provided by the embodiment of the invention is stable. In addition, the nickel mononuclear hydrogenase model provided by the embodiment of the invention adopts cheap metal nickel, so that the cost can be reduced, and the economy is realized.
The preparation method of the nickel mononuclear hydrogenase model substance has mild reaction conditions and is easy to implement; the yield of the nickel mononuclear hydrogenase model prepared by the embodiment of the invention is high and is 90-95%, and the yield of the nickel mononuclear intermediate prepared by the embodiment of the invention is high and is 85-93%.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
FIG. 1 is a crystal structure diagram of a model nickel mononuclear hydrogenase according to an embodiment of the present invention;
FIG. 2 is a phosphorus spectrum of an intermediate product of nickel mononuclear species provided in example 1;
FIG. 3 is a phosphorus spectrum of the nickel mononuclear hydrogenase model provided in example 2;
FIG. 4 is a hydrogen spectrum of the model nickel mononuclear hydrogenase provided in example 2;
FIG. 5 is an electrocatalytic hydrogen production diagram of the model nickel mononuclear hydrogenase provided in example 3.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The first aspect of the embodiments of the present invention provides a nickel mononuclear hydrogenase model, wherein the chemical structural formula of the hydrogenase model is as follows:
the chemical formula of the nickel mononuclear hydrogenase model substance is (dppe) Ni [ NS ]]BF4The nickel mononuclear hydrogenase model is an ionic compound; wherein the nickel mononuclear hydrogenase model substance is a center which takes a nickel Ni atom as a structural unit, and the nickel atom is connected with a diphosphine ligand dppe and a bidentate nitrogen-sulfur ligand [ NS ]]The cationic complex is formed together, the cationic complex has a positive charge, and the cationic complex resists a tetrafluoroborate anion to achieve charge balance. Bidentate nitrogen sulfur ligand [ NS]The nickel mononuclear hydrogenase model substance has catalytic activity and is a good enzyme-imitating model catalyst.
Wherein the diphosphine ligand dppe is 1, 2-bis (diphenylphosphinoethane), and the chemical structural formula is as follows:
the bidentate nitrogen sulfur ligand [ NS ] is 8-quinoline thiol, and the chemical structural formula is as follows:
referring to fig. 1, fig. 1 shows a crystal structure diagram of a model of a nickel mononuclear hydrogenase according to an embodiment of the present invention, wherein the center of the nickel atom is tetracoordinate and assumes a planar configuration. The crystal structure of the nickel mononuclear hydrogenase model substance provided by the embodiment of the invention is stable.
In addition, the nickel mononuclear hydrogenase model provided by the embodiment of the invention adopts cheap metal nickel, so that the cost can be reduced, and the economy is realized.
The second aspect of the embodiments of the present invention provides a nickel mononuclear intermediate product, where a chemical structural formula of the nickel mononuclear intermediate product is as follows:
wherein, the nickel mononuclear intermediate product takes a nickel atom as the center of a structural unit, the nickel atom is respectively connected with a diphosphine ligand and a bidentate nitrogen-sulfur ligand [ NS ], and the nickel Ni atom and the chlorine Cl atom are connected in a metal bond form; the diphosphine ligand is 1, 2-bis (diphenylphosphinoethane), and the bidentate nitrogen-sulfur ligand [ NS ] is 8-quinoline thiol.
As can be seen from the chemical structural formulas shown in the above examples, the intermediate product of the nickel mononuclear class and the hydrogenase model of the nickel mononuclear class have a common structural unit, the common structural unit comprises a center which takes a nickel atom as a structural unit, and the nickel atom is respectively connected with a diphosphine ligand and a bidentate nitrogen-sulfur ligand [ NS ].
In view of the nickel mononuclear intermediate product described in the foregoing embodiment, a third aspect of the embodiments of the present invention provides a method for preparing the nickel mononuclear intermediate product, including the following steps:
s100, preparing the intermediate product of the nickel mononuclear
Step S100 specifically includes the following steps:
s101, adding Ni (dppe) Cl2Dissolving in a first organic solvent to obtain Ni (dppe) Cl2A solution; wherein Ni (dppe) Cl2The chemical structural formula of (A) is:
s102, dissolving 8-quinoline sodium thiol in a first organic solvent to obtain an 8-quinoline sodium thiol solution; wherein the chemical structural formula of the 8-quinoline sodium mercaptide is as follows:
s103, adding the 8-quinoline sodium mercaptide solution into Ni (dppe) Cl2Carrying out coordination and ion exchange reaction in the solution, removing sodium chloride (NaCl) generated in the reaction process, and carrying out reduced pressure concentration to obtain a nickel mononuclear intermediate product; wherein the sodium 8-quinolinethiol and the Ni (dppe) Cl2The ratio of the amounts of substances (1): 0.8 to 1.3; preferably, said sodium 8-quinolinethiol and said Ni (dppe) Cl2The ratio of the amounts of the substances of (a) may be any of the following ratios, for example 1: 0.8,1: 0.9,1: 1,1: 1.1,1: 1.2 or 1: 1.3; most preferably, said sodium 8-quinolinethiol and said Ni (dppe) Cl2The ratio of the amounts of substances (1): 1.
preferably, in step S101 and step S102, the first organic solvent may be dichloromethane (abbreviated as DCM) or tetrahydrofuran THF.
The reaction process of step S103 is as follows:
in any of steps S101 to S103, the dissolution temperature or the reaction temperature may be room temperature, or may be any of 15 ℃ to 45 ℃, such as any of 15 ℃, 20 ℃, 25 ℃, 28 ℃, 30 ℃, 35 ℃, 38 ℃, 40 ℃, 42 ℃ or 45 ℃.
Specifically, Ni (dppe) Cl is added in step S1012The temperature for dissolving in the first organic solvent may be set to room temperature or any one of 15 ℃ to 45 ℃;
the temperature for dissolving the 8-quinolinethiol sodium in the first organic solvent in the step S102 may be set to room temperature or any one of 15 ℃ to 40 ℃;
step S103, adding Ni (dppe) Cl into 8-quinoline sodium mercaptide solution2The reaction temperature for carrying out the reaction in the solution may be set to room temperature or any one of 15 ℃ to 40 ℃.
The reaction condition for preparing the nickel mononuclear intermediate product is mild and easy to implement; the spontaneous reaction can be realized without adding an additional heat source; the yield of the intermediate product of the nickel mononuclear type prepared by the embodiment of the invention is high and is 85-93%.
In view of the nickel mononuclear hydrogenase model according to the above embodiments, a fourth aspect of the embodiments of the present invention provides a method for preparing the nickel mononuclear hydrogenase model, comprising the following steps:
s200, preparing a nickel mononuclear hydrogenase model substance
Step S200 specifically includes the following steps:
under nitrogen N2And under the protection of light, adding the intermediate product of the nickel mononuclear class prepared in the step S103 into a second organic solvent for dissolving, and adding AgBF4Mixing, dissolving and reacting, wherein a metal bond between Ni and chlorine is broken in the reaction process; after the reaction, removing AgCl generated in the reaction process, and removing the second organic solvent by decompression concentration to obtain a nickel mononuclear hydrogenase model substance; wherein the nickel mononuclear intermediate and the AgBF4The ratio of the amounts of substances (1): 0.8 to 1.3. Preferably, said nickel mononuclear intermediate and said AgBF4Of the amount of substanceThe ratio may be any of the following ratios, for example 1: 0.8,1: 0.9,1: 1,1: 1.1,1: 1.2 or 1: 1.3; most preferably, said nickel mononuclear intermediate and said AgBF4The ratio of the amounts of substances (1): 1.
preferably, the second organic solvent may be anhydrous acetonitrile (methycy anide, abbreviated as MeCN) or anhydrous acetone.
The reaction process of step S200 is as follows:
in step S200, the reaction temperature for preparing the nickel mononuclear hydrogenase model may be room temperature, or any temperature of 15 to 45 ℃, such as any temperature of 15 ℃, 20 ℃, 25 ℃, 28 ℃, 30 ℃, 35 ℃, 38 ℃, 40 ℃, 42 ℃ or 45 ℃.
Specifically, in step S200, the temperature at which the nickel mononuclear intermediate prepared in step S103 is added to the second organic solvent and dissolved may be room temperature or any temperature of 15 to 45 ℃,
adding AgBF4The temperature for mixing, dissolving and reacting may be room temperature or any temperature of 15 to 45 ℃.
The reaction conditions of the embodiment of the invention are mild and easy to implement; the nickel mononuclear hydrogenase model prepared by the embodiment of the invention has high yield which is 90-95%. The nickel mononuclear hydrogenase model substance has catalytic activity and is a good enzyme-simulated model catalyst.
Aiming at the characteristic that the nickel mononuclear hydrogenase model has catalytic activity, the fifth aspect of the embodiment of the invention provides the application of the nickel mononuclear hydrogenase model in electrocatalysis of protonic acid reduction to hydrogen. The embodiment of the invention is used for electrocatalytic hydrogen production and has better hydrogen production efficiency. TOF value range of hydrogen production is 1.6s-1～181.8s-1。
The invention is further illustrated by the following specific examples:
example 1
A nickel mononuclear intermediate product is prepared by the following steps:
526mg of 1mmol of Ni (dppe) Cl2Into a 250mL Schlenk flask containing magnetons, 100mL of methylene chloride was added and dissolved with stirring at room temperature to obtain Ni (dppe) Cl2A solution;
183mg, i.e. 1mmol, of sodium 8-quinolinethiol were dissolved in 30mL of dichloromethane to obtain a solution of sodium 8-quinolinethiol;
then 1mmol of a solution of sodium 8-quinolinethiol was added dropwise to 1mmol of Ni (dppe) Cl2And (3) stirring the solution at room temperature for 2.5h after the dropwise addition is finished, filtering to remove NaCl generated in the reaction process, concentrating the solution to 20mL under reduced pressure, and adding 50mL of n-hexane to separate out the intermediate products in the nickel mononuclear class.
The nickel mononuclear intermediate was a reddish brown precipitate with a yield of 604mg and a yield of 93%.
With reference to fig. 2, fig. 2 shows a phosphorus spectrum of the nickel mononuclear intermediate product provided in example 1, and the characterization data of the nickel mononuclear intermediate product are as follows:31P{1h } NMR (202MHz, DCM), s peak, 59.45 ppm.
Example 2
A nickel mononuclear hydrogenase model substance is prepared by the following steps:
in N2And taking 650mg in total of the nickel mononuclear intermediate prepared in example 1 several times under protection from light, adding 650mg, namely 1mmol of the nickel mononuclear intermediate prepared in example 1 into a magneton-containing 100mLSchlenk bottle, dissolving in 60mL of anhydrous acetonitrile, and then adding 195mg, namely 1mmol of AgBF4And stirring for 15min at room temperature, filtering to remove AgCl generated in the reaction process, and performing vacuum pumping to remove anhydrous acetonitrile to obtain the nickel mononuclear hydrogenase model substance.
Wherein the nickel mononuclear hydrogenase model substance is bright red solid, the yield is 665mg, and the yield is 95%.
Referring to FIGS. 3 and 4, FIG. 3 is a phosphorus spectrum of a nickel mononuclear hydrogenase model provided in example 2; FIG. 4 is a hydrogen spectrum of the model nickel mononuclear hydrogenase provided in example 2, which is characterized by the following data:1HNMR(500MHz，CD3CN)：δ8.48-7.14(m，26H，C6H5 or C9H6NS)，2.58-2.48(m，4H，PCH2),31P{1H}NMR(202MHz，CD3CN): dd peak, 61,55 ppm.
Example 3
The electrocatalytic proton reduction hydrogen production reaction of the nickel mononuclear hydrogenase model prepared in the example 2 has the following catalytic process:
in N2Under protection, a CHI760e electrochemical workstation is used, a three-electrode system with a glassy carbon electrode as a working electrode, a platinum electrode as an auxiliary electrode and a silver electrode as a reference electrode is adopted, and n-Bu4NBF4As a supporting electrolyte.
3.5mg, namely 0.005mmol of the nickel mononuclear hydrogenase model prepared in the embodiment 2 is placed in an electrochemical cell, dissolved in 5mL of acetonitrile, and scanned once with a cyclic voltammetry curve every 1 muL of acetic acid at a scanning speed of 100mV/s until the hydrogen production current intensity reaches the maximum value.
Referring to fig. 5, fig. 5 is an electrocatalytic hydrogen production diagram of the nickel mononuclear hydrogenase model provided in example 3. As shown in fig. 5, the cyclic voltammetry curve of the nickel mononuclear hydrogenase model has two sets of redox couples, and the proton reduction of acetic acid to produce hydrogen occurs in the second set of redox couples, so that the hydrogen production current intensity is increased. The hydrogen production current continuously rises along with the increase of the hydrogen proton concentration, and finally the catalytic current reaches the maximum value after 17 mu L of acetic acid is added. TOF is calculated to be 181.8s-1The nickel mononuclear hydrogenase model substance has good catalytic hydrogen production efficiencyAnd (5) fruit.
Example 4
Nickel mononuclear intermediate product
In contrast to example 1, example 4 replaced dichloromethane with tetrahydrofuran; the reaction procedure in example 4 included the following steps:
the yield of the intermediate product of nickel mononuclear type prepared in example 4 was 552.5mg, which was 85%.
Example 5
Nickel mononuclear intermediate product
In contrast to example 1, in example 1mmol of sodium 8-quinolinethiol solution were added dropwise to 1mmol of Ni (dppe) Cl2Stirring the solution at room temperature for 2.5h after the dropwise addition is finished; example 5A 1mmol solution of sodium 8-quinolinethiol was added dropwise to a 1mmol solution of Ni (dppe) Cl2Stirring the solution at room temperature for 5 hours after the dropwise addition is finished;
the yield of the nickel mononuclear intermediate prepared in example 5 was 604mg, and the yield was 93%.
Example 6
Nickel mononuclear intermediate product
In contrast to example 1, 1mmol of the sodium 8-quinolinethiol solution of example 1 was added dropwise to 1mmol of Ni (dppe) Cl2In solution; EXAMPLE 61 mmol of sodium 8-quinolinethiol solution dropwise to 0.8mmol of Ni (dppe) Cl2In the solution, the solution is added with a solvent,
the yield of the nickel mononuclear intermediate prepared in example 6 was 565.5mg, which was 87%.
Example 7
Nickel mononuclear intermediate product
In contrast to example 1, 1mmol of the sodium 8-quinolinethiol solution of example 1 was added dropwise to 1mmol of Ni (dppe) Cl2In solution; EXAMPLE 7 1mmol of sodium 8-quinolinethiol solution dropwise to 1.3mmol of Ni (dppe) Cl2In the solution, the solution is added with a solvent,
the yield of the nickel mononuclear intermediate prepared in example 7 was 578.5mg, which was 89%.
Example 8
Nickel mononuclear intermediate product
In contrast to example 1, 1mmol of the sodium 8-quinolinethiol solution of example 1 was added dropwise to 1mmol of Ni (dppe) Cl2In solution; EXAMPLE 81 mmol of sodium 8-quinolinethiol solution dropwise to 1.1mmol of Ni (dppe) Cl2In the solution, the solution is added with a solvent,
the yield of the nickel mononuclear intermediate prepared in example 8 was 585mg, and 90%.
Example 9
Nickel mononuclear hydrogenase model substance
In contrast to example 2, anhydrous acetonitrile was replaced with anhydrous acetone in example 9; the reaction procedure in example 9 included the following steps:
the yield of the model nickel mononuclear hydrogenase prepared in example 9 was 658mg, 94%.
Example 10
Nickel mononuclear hydrogenase model substance
In contrast to example 2, example 2 added AgBF4Stirring at room temperature for 15 min; example 10 AgBF addition4Stirring at 40 deg.C for 15 min; the yield of the model nickel mononuclear hydrogenase prepared in example 10 was 658mg, 94%.
Example 11
Nickel mononuclear hydrogenase model substance
In contrast to example 2, the starting material in example 2 was 1mmol of the nickel mononuclear intermediate prepared in example 1, and 1mmol of AgBF4(ii) a The starting material in example 11 was 1mmol of the nickel mononuclear intermediate prepared in example 1Product, and 1.3mmol of AgBF4；
The yield of the nickel mononuclear hydrogenase model prepared in example 11 was 644mg, and the yield was 92%.
Example 12
Nickel mononuclear hydrogenase model substance
In contrast to example 2, the starting material in example 2 was 1mmol of the nickel mononuclear intermediate prepared in example 1, and 1mmol of AgBF4(ii) a The starting material in example 12 was 1mmol of the nickel mononuclear intermediate prepared in example 1, and 0.8mmol of AgBF4；
The nickel mononuclear hydrogenase model prepared in example 12 was produced in a yield of 630mg and 90%.
Example 13
Nickel mononuclear hydrogenase model substance
In contrast to example 2, the starting material in example 2 was 1mmol of the nickel mononuclear intermediate prepared in example 1, and 1mmol of AgBF4(ii) a The starting material in example 13 was 1mmol of the nickel mononuclear intermediate prepared in example 1, and 1.2mmol of AgBF4；
The yield of the model nickel mononuclear hydrogenase prepared in example 13 was 637mg and 91%.
Example 14
Different from the embodiment 3, the nickel mononuclear hydrogenase model prepared in the embodiment 9 is adopted for electrocatalytic proton reduction hydrogen production reaction; TOF of example 14 was 179.5s-1。
Example 15
Different from the embodiment 3, the nickel mononuclear hydrogenase model prepared in the embodiment 10 is adopted for electrocatalytic proton reduction hydrogen production reaction; TOF of example 15 was 178.6s-1。
Example 16
Different from the embodiment 3, the nickel mononuclear hydrogenase model prepared in the embodiment 11 is adopted for electrocatalytic proton reduction hydrogen production reaction; example 16 ofTOF of 152.1s-1。
Example 17
Different from the embodiment 3, the nickel mononuclear hydrogenase model prepared in the embodiment 12 is adopted for electrocatalytic proton reduction hydrogen production reaction; TOF of example 17 was 163.6s-1。
Example 18
Different from the embodiment 3, the nickel mononuclear hydrogenase model prepared in the embodiment 13 is adopted for electrocatalytic proton reduction hydrogen production reaction; TOF of example 18 was 167.8s- 1。
The present invention has been described in further detail with reference to the specific embodiments thereof, and it should be understood that the foregoing is only illustrative of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, but rather that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.
Claims (9)
1. A nickel mononuclear hydrogenase model substance, which is characterized in that the chemical structural formula of the nickel mononuclear hydrogenase model substance is as follows:
wherein, the nickel mononuclear hydrogenase model is an ionic compound, a nickel atom is taken as the center of a structural unit, a diphosphine ligand and a bidentate nitrogen-sulfur ligand [ NS ] are respectively connected to the nickel atom to jointly form a cationic complex, the cationic complex has a positive charge, and the cationic complex counter-balances a tetrafluoroborate anion; the diphosphine ligand is 1, 2-bis (diphenylphosphinoethane), and the bidentate nitrogen-sulfur ligand [ NS ] is 8-quinoline thiol.
2. A nickel mononuclear intermediate product, which is characterized in that the chemical structural formula of the nickel mononuclear intermediate product is as follows:
wherein, the nickel mononuclear intermediate product takes a nickel atom as the center of a structural unit, the nickel atom is respectively connected with a diphosphine ligand and a bidentate nitrogen-sulfur ligand [ NS ], and the nickel atom is connected with a chlorine atom in a metal bond form; the diphosphine ligand is 1, 2-bis (diphenylphosphinoethane), and the bidentate nitrogen-sulfur ligand [ NS ] is 8-quinoline thiol.
3. A method for preparing the nickel mononuclear intermediate product according to claim 2, comprising the steps of:
under room temperature, adding Ni (dppe) Cl2Dissolving in a first organic solvent to obtain Ni (dppe) Cl2A solution; dissolving 8-quinolinethiol sodium in a first organic solvent to obtain a 8-quinolinethiol sodium solution;
(iii) dropwise adding the sodium 8-quinolinethiol solution to the Ni (dppe) Cl2In the solution, removing sodium chloride generated in the reaction process, and concentrating under reduced pressure to obtain a nickel mononuclear intermediate product; wherein the sodium 8-quinolinethiol and the Ni (dppe) Cl2The ratio of the amounts of substances (1): 0.8 to 1.3.
4. The method for preparing a nickel mononuclear intermediate product according to claim 3, wherein the sodium 8-quinolinethiol and the Ni (dppe) Cl are added2The ratio of the amounts of substances (1): 1.
5. the method according to claim 3, wherein the first organic solvent is dichloromethane or tetrahydrofuran.
6. A method for preparing the nickel mononuclear hydrogenase model according to claim 1, comprising the steps of:
under the protection of nitrogen and light, the nickel mononuclear prepared by the method of claim 3Adding the intermediate product into a second organic solvent for dissolving at room temperature, and adding AgBF4Mixing, dissolving and reacting; after the reaction, removing AgCl generated in the reaction process, and removing the second organic solvent by decompression concentration to obtain a nickel mononuclear hydrogenase model substance; wherein the nickel mononuclear intermediate and the AgBF4The ratio of the amounts of substances (1): 0.8 to 1.3.
7. The method of claim 6, wherein the intermediate product of the nickel mononuclear hydrogenase and the AgBF are produced by reacting the intermediate product of the nickel mononuclear type with the AgBF4The ratio of the amounts of substances (1): 1.
8. the method for preparing a nickel mononuclear hydrogenase model according to claim 6 wherein the second organic solvent is anhydrous acetonitrile or anhydrous acetone.
9. Use of a nickel mononuclear hydrogenase model according to claim 1 for electrocatalytic reduction of protonic acid to hydrogen.
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