CN108912179B - 一种含mnt配体的单核镍配合物作为电催化制氢催化剂的应用 - Google Patents
一种含mnt配体的单核镍配合物作为电催化制氢催化剂的应用 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 38
- 239000001257 hydrogen Substances 0.000 title claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000003446 ligand Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 title claims abstract description 16
- -1 N-substituted bis (diphenylphosphino) ammonia Chemical class 0.000 claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 63
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 14
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 10
- 238000004809 thin layer chromatography Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- DMDOIBWPFWJPQJ-ONEGZZNKSA-N (e)-2,3-bis(sulfanyl)but-2-enedinitrile Chemical class N#CC(/S)=C(\S)C#N DMDOIBWPFWJPQJ-ONEGZZNKSA-N 0.000 claims 1
- LDKSCZJUIURGMW-UHFFFAOYSA-N 1-isothiocyanato-3-methylsulfanylpropane Chemical group CSCCCN=C=S LDKSCZJUIURGMW-UHFFFAOYSA-N 0.000 claims 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- AVYXASMIUOIQII-UHFFFAOYSA-N [(diphenylphosphanylamino)-phenylphosphanyl]benzene Chemical class C=1C=CC=CC=1P(C=1C=CC=CC=1)NP(C=1C=CC=CC=1)C1=CC=CC=C1 AVYXASMIUOIQII-UHFFFAOYSA-N 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 1
- 150000002815 nickel Chemical group 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 10
- 238000001308 synthesis method Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000011161 development Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 108010020056 Hydrogenase Proteins 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000003115 supporting electrolyte Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- QSLPNSWXUQHVLP-UHFFFAOYSA-N $l^{1}-sulfanylmethane Chemical compound [S]C QSLPNSWXUQHVLP-UHFFFAOYSA-N 0.000 description 1
- KYPOHTVBFVELTG-UPHRSURJSA-N (z)-but-2-enedinitrile Chemical compound N#C\C=C/C#N KYPOHTVBFVELTG-UPHRSURJSA-N 0.000 description 1
- 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 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical class [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910018502 Ni—H Inorganic materials 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- XQJHRCVXRAJIDY-UHFFFAOYSA-N aminophosphine Chemical compound PN XQJHRCVXRAJIDY-UHFFFAOYSA-N 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 210000000080 chela (arthropods) Anatomy 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 125000004373 methylthiopropyl group Chemical group [H]C([H])([H])SC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VOKXPKSMYJLAIW-UHFFFAOYSA-N nickel;phosphane Chemical compound P.[Ni] VOKXPKSMYJLAIW-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 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 System
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
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- B01J35/33—
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
本发明属于催化剂制备领域，具体为一种单核镍配合物作为电催化制氢催化剂的应用，该电催化制氢催化剂为含N‑取代双(二苯基膦基)氨(R‑PNP)和马来腈二硫醇盐(mnt2‑)配体的单核镍配合物，该配合物是由R‑PNP和马来腈二硫醇盐配体与金属镍原子连接而成的一种单核镍配合物，其化学结构如下：
该镍配合物在酸性介质表现出高效的电催化制氢活性。本发明的单核镍配合物的合成方法简单、反应条件温和、产率高等优点，可适合于具有催化制氢性能的系列含N‑取代双(二苯基膦基)氨和马来腈二硫醇盐配体的单核镍配合物的合成，在氢能源开发有潜在的应用价值。
Description
技术领域
本发明涉及催化剂制备技术领域，具体为一种由N-取代双(二苯基膦基) 氨(R-PNP)和马来腈二硫醇盐(mnt2-)配体与金属镍原子连接而成的一种金 属配合物作为电催化制氢催化剂的应用。
背景技术
随着社会经济的高速发展，能源危机变得日益突出，因此开发一种具有高 效制氢活性的催化剂变得越来越重要。众所周知，地球上已开发的自然资源基 本上为不可再生的、且常具有一定污染性的资源。而氢能源具有燃烧热值高和 无污染的特点，致使氢能源的开发格外受到各国政府和科学家们的高度重视。 制氢途径主要包括化石燃料裂解、水电解和生物制氢。生物制氢是利用微生物 体内存在的一种生物酶所进行的制氢。氢化酶作为微生物体内一种能够高效可 逆催化氢气氧化和质子还原的金属蛋白酶，氢化酶可分为[铁铁]氢化酶、[镍铁] 氢化酶和单金属氢化酶，它们具有高效、绿色、能耗低、污染小的特点。单金 属氢化酶具有合成方法简单、成本相对较低的优点，为此人们开展了作为氢化 酶模型物的单核镍配合物的研究。单核镍配合物通常含有螯合双齿配体(如双 膦(P∩P)、双氮(N∩N)或氮膦(N∩P)化合物等(S.A.Burgess,A.J.Kendall,D.R. Tyler,etal.Hydrogenation of CO2in water usinga bis(diphosphine)Ni-H complex. ACSCatal.,2017,7(4):3089-3096.A.Jain,M.L.Reback,M.L.Lindstrom,et al.Investigatingthe role of the outer-coordination sphere in[Ni(P(Ph)2N(PhR)2)2]2+hydrogenase mimics.Inorg.Chem.,2012,51(12):6592-6602；J.Wenz,A.Kochan,H.Wadepohl,et al.A readily accessible chiral NNN pincer ligand with a pyrrolebackbone and its Ni(II)chemistry:Syntheses,structural chemistry,and bondactivations.Inorg. Chem.,2017,56(6):3631-3643；P.Hao,S.J.Song,T.P.F.Xiao,etal.Highly active 8- benzoxazolyl-or 8-benzo-thiazolyl-2-alkylquinolinylnickel(II)complexes for ethylene dimeriza-tion and vinyl polymerization ofnorbornene.Polyhedron,2013,52:1138-1144； G.C.Stephan,C.Nather,C.Sivasankar,etal.Mo–and W–N2and–CO complexes with novel mixed P/N ligands:Structuralproperties and implications to synthetic nitrogen fixation.Inorg.Chim.Acta,2008,361:1008-1019；P.W.Dyer,J.Fawcett,M.J. Hanton.Rigid N-phosphino guanidineP,N ligands and their use in nickel-catalyzed ethyleneoligomerization.Organometal.,2008,27(19):5082-5087；Z.Guan,W.J.Marshall.Synthesis of new phosphine imine ligands and their effects on thethermal stability of late-transition-metal olefin polymerizationcatalysts.Organometal.,2002, 21(17):3580-3586)。这些螯合配体所形成的过渡金属配合物常作为烯烃齐聚化 反应和聚合反应的高效的催化剂，近来发现部分单核镍配合物还具有催化质子 还原制氢活性。
N-取代双(二苯基膦基)氨(R-PNP)是一类新颖的氮杂螯合双膦配体，通 过引入硫醇盐或二硫醇盐配体，可用于混合配体的单核金属配合物和双核金属 配合物的合成(X.F.Liu,X.Li,J.Yan.Synthetic and structural studies of the mononuclearnickel(II)ethanedithiolate complexes with chelating N-substituted bis(diphenylphosphanyl)amine.Polyhedron,2015,85:482-487；X.F.Liu.Condensationreactions of the mononuclear nickel(II)complexes[RN(PPh2)2]NiCl2with 1,2-ethanedithiol or 1,3-propanedithiol.Inorg.Chim.Acta,2014,421:10-17；L.C.Song,J.P. Li,Z.J.Xie,et al.Synthesis,structural characterization,andelectrochemical properties of dinuclear Ni/Mn model complexes for active siteof[NiFe]-hydrogenases.Inorg.Chem.,2013,52(19):11618-11626)，但这些金属配合物的催化制氢性能研究相对 较少，Gan等研究发现：含1,2-双(二苯基膦乙烷)和邻苯二硫酚盐配体的单核 镍配合物(dppe)Ni(bdt)无论是在醋酸还是在对甲苯磺酸介质中均没有电催化制氢 活性(L.Gan,T.L.Groy,P.Tarakeshwar,et al,A nickel phsphine complex as afast and efficient hydrogen production catalyst.J.Am.Chem.Soc.,2015,137(3),1109- 1115)。
具有离域化π电子系统的马来腈二硫醇盐是一类配位能力非常强的双齿二 硫醇盐配体，其均配型金属配合物(R4N)m[M(mnt)2]n具有良好的光学、电学和磁 学特性，对它们的研究十分活跃。最近Peng等发现马来腈二硫醇盐的异构体2,2- 二氰基乙烯-1,1-二硫醇盐(i-mnt2-)的单核镍的均配型配合物[BzPyN(CH3)2]2[Ni(i- mnt)2]在水中可作为光催化和电催化制氢催化剂(Q.-X.Peng,D.Xue,S.-Z.Zhan,et al.Visible-light-drivenphotocatalytic system based on a nickel complex over CdS materials forhydrogen production from water.Appl.Catal.B:Environm.,2017,219, 353-361)。
开发出具有催化制氢性能的合成方法简便、反应条件温和的单核金属氢 化酶模型物配合物对缓解日益严重的能源危机具有重要的现实意义。本发明 的含N-取代双(二苯基膦基)氨和马来腈二硫醇盐配体的单核镍混配型配合物 (R-PNP)Ni(mnt)未见报道，它们具有高效的电催化制氢活性。
发明内容
本发明基于以上技术问题，提供一种由N-取代双(二苯基膦基)氨(R- PNP)和马来腈二硫醇盐(mnt2-)配体与金属镍原子连接而成的一种金属配合 物以及其作为电催化制氢催化剂的应用。该合成方法简便、产率高，其可作为 电催化制氢催化剂，在氢能源开发领域有潜在的工业应用价值。
本发明的具体技术方案如下：
一种含N-取代双(二苯基膦基)氨配体和马来腈二硫醇盐配体的单核镍配 合物，它是由N-取代双(二苯基膦基)氨配体和马来腈二硫醇盐配体与金属镍原 子连接而成的一种单核镍配合物，其化学结构式如下：
该单核镍配合物的合成方法为：
1)将R-N(PPh2)2NiCl2和Na2mnt与有机溶剂混合，在20-40℃下搅拌反应 1-3小时，得橙红色溶液；所述有机溶剂为三氯甲烷或二氯甲烷，R- N(PPh2)2NiCl2、Na2mnt和有机溶剂的用量比为：1mmol:1mmol:20-30mL。
2)采用旋转蒸发仪减压除去溶剂，用二氯甲烷溶解，以二氯甲烷和甲醇 的混合溶剂作展开剂进行薄层色谱分离，收集橙红色带，洗脱后得橙红色的单 核镍配合物。
所述展开剂二氯甲烷和甲醇的体积比例为10：1-20：1和1：0，薄层色谱 分离所需硅胶板的规格为26×20×0.25cm3。
合成的反应式为：
R＝CH2CH2CH2OCH3,CH2CH2CH2SCH3,CH(CH3)Ph,CH2CH2CH(CH3)2,C6H4CH3-p。
本发明的积极效果体现在：
(一)现已公开的单核镍配合物与本发明的单核镍配合物的结构不同，本 发明所制备的单核镍配合物为混配型新化合物。
(二)本发明的合成方法简单、反应条件温和、合成产率高，适合于多种 含R-PNP和马来腈二硫醇盐配体的单核镍配合物的合成。
(三)本发明的单核镍配合物，在醋酸、三氟乙酸和对甲苯磺酸酸性介质 中分别具有催化还原质子制氢的性能，因此本发明的单核镍配合物具有潜在的 工业应用价值。
附图说明
图1为实施例1中的(CH3O(CH2)3N(PPh2)2)Ni(mnt)的核磁共振氢谱；
图2为实施例1中的(CH3O(CH2)3N(PPh2)2)Ni(mnt)的核磁共振碳谱；
图3为实施例1中的(CH3O(CH2)3N(PPh2)2)Ni(mnt)的核磁共振磷谱；
图4为实施例6中的(CH3O(CH2)3N(PPh2)2)Ni(mnt)添加醋酸的循环伏安 图；
图5为实施例7中的(CH3O(CH2)3N(PPh2)2)Ni(mnt)添加三氟乙酸的循环伏 安图；
图6为实施例8中的(CH3O(CH2)3N(PPh2)2)Ni(mnt)添加对甲苯磺酸的循环 伏安图；
具体实施方式
下面结合具体实施例和比较例进一步阐述本发明。应理解为，这些实施例 仅用于说明本发明而不用于限制本发明的范围。此外应理解为，在阅读了本发 明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等 价形式同样落于本申请所附权利要求书所限定的范围。
实施例1：
一种含N-取代双(二苯基膦基)氨和马来腈二硫醇盐配体的单核镍配合物， 所述单核镍配合物的化学式为(CH3O(CH2)3N(PPh2)2)Ni(mnt)，反应方程式如下：
所述的含N-取代双(二苯基膦基)氨和马来腈二硫醇盐配体的单核镍配合物的合成方法如下：
在装有磁力搅拌子的圆底烧瓶中，将0.1860g Na2mnt(1mmol)、0.5870g (CH3O(CH2)3N(PPh2)2)NiCl2(1mmol)和20mL二氯甲烷混合，在室温下搅拌反 应3小时，得橙红色溶液。用2×20mL水洗除去NaCl，无水MgSO4干燥，旋 转蒸发仪减压除去有机溶剂，用适量二氯甲烷溶解，以体积比为10:1的二氯甲 烷:甲醇作展开剂进行薄层色谱分离，收集橙红色带，洗脱后得0.5738g，产率 88％。1H NMR(400MHz,CDCl3):1.31-1.37(m,2H,CH2),2.93(t,J＝6.0Hz,2H, CH2N),3.00-3.10(m,5H,CH3OCH2),7.52(t,J＝8.0Hz,8H,m-PhH),7.62(t,J＝6.0Hz, 4H,p-PhH),7.76-7.81(q,J＝6.0Hz,8H,o-PhH)ppm.13C NMR(100.6MHz,CDCl3):29.82(s,CH2),46.15(t,J＝9.1Hz,CH2N),58.73(s,OCH3),69.32(s,OCH2),116.47(s, SC＝CS),126.62(t,4JP-C＝11.6Hz,p-PhC),128.81(t,3JP-C＝24.6Hz,m-PhC).129.59(t, 2JP-C＝5.5Hz,o-PhC).133.04(t,1JP-C＝6.0Hz,i-PhC).133.34(s,CN)ppm.31P NMR (161.9MHz,CDCl3,85％H3PO4):58.32(s,P,NP2)ppm。其核磁共振谱图见图1-图 3所示。
实施例2：
一种含N-取代双(二苯基膦基)氨和马来腈二硫醇盐配体的单核镍配合物， 所述单核镍配合物的化学式为(CH3S(CH2)3N(PPh2)2)Ni(mnt)，其化学结构式如 下：
所述的含N-取代双(二苯基膦基)氨和马来腈二硫醇盐配体的单核镍配合物的合成方法如下：
在装有磁力搅拌子的圆底烧瓶中，将0.1860g Na2mnt(1mmol)、0.6030g (CH3S(CH2)3N(PPh2)2)NiCl2(1mmol)和20mL二氯甲烷混合，在室温下搅拌反应 3小时，得橙红色溶液。用2×20mL水洗除去NaCl，无水MgSO4干燥，旋转 蒸发仪减压去除有机溶剂，用适量二氯甲烷溶解，以20:1的二氯甲烷和甲醇混 合液作展开剂进行薄层色谱分离，收集橙红色带，洗脱后得0.6365g，产率 95％。
实施例3：
一种含N-取代双(二苯基膦基)氨和马来腈二硫醇盐配体的单核镍配合物， 所述单核镍配合物的化学式为(CH3CHPhN(PPh2)2)Ni(mnt)，其化学结构式如 下：
所述的含N-取代双(二苯基膦基)氨和马来腈二硫醇盐配体的单核镍配合物的合成方法如下：
在装有磁力搅拌子的圆底烧瓶中，将0.1860g Na2mnt(1mmol)、0.6190g (CH3CHPhN(PPh2)2)NiCl2(1mmol)和20mL三氯甲烷混合，在室温下搅拌反应3 小时，得橙红色溶液。用2×20mL水洗除去NaCl，无水MgSO4干燥，旋转蒸 发仪减压去除有机溶剂，用适量二氯甲烷溶解，以10:1的二氯甲烷和甲醇混合 液作展开剂进行薄层色谱分离，收集橙红色带，洗脱后得0.6117g，产率 89％。
实施例4：
一种含N-取代双(二苯基膦基)氨和马来腈二硫醇盐配体的单核镍配合物， 所述单核镍配合物的化学式为(CH3)2CH(CH2)2N(PPh2)2)Ni(mnt)，其化学结构式 如下：
所述的含N-取代双(二苯基膦基)氨和马来腈二硫醇盐配体的单核镍配合物的合成方法如下：
在装有磁力搅拌子的圆底烧瓶中，将0.1860g Na2mnt(1mmol)、0.5840g (CH3)2CH(CH2)2N(PPh2)2)NiCl2(1mmol)和20mL二氯甲烷混合，在室温下搅拌反 应3小时，得橙红色溶液。用2×20mL水洗除去NaCl，无水MgSO4干燥，旋 转蒸发仪减压去除有机溶剂，用适量二氯甲烷溶解，以二氯甲烷：甲醇＝12:1 作展开剂进行薄层色谱分离，收集橙红色带，洗脱后得0.5548g，产率85％。
实施例5：
一种含N-取代双(二苯基膦基)氨和马来腈二硫醇盐配体的单核镍配合物， 所述单核镍配合物的化学式为(p-CH3-PhN(PPh2)2)Ni(mnt)，其化学结构式如下：
所述的含N-取代双(二苯基膦基)氨和马来腈二硫醇盐配体的单核镍配合物的合成方法如下：
在装有磁力搅拌子的圆底烧瓶中，将0.1860g Na2mnt(1mmol)、0.6050g(p- CH3-PhN(PPh2)2)NiCl2(1mmol)和20mL二氯甲烷混合，在室温下搅拌反应3小 时，得橙红色溶液。用2×20mL水洗除去NaCl，无水MgSO4干燥，旋转蒸发 仪减压去除有机溶剂，用适量二氯甲烷溶解，以二氯甲烷作展开剂进行薄层色 谱分离，收集橙红色带，洗脱后得0.5825g，产率87％。
实施例6：
本实施例提供了单核镍配合物(CH3O(CH2)3N(PPh2)2)Ni(mnt)在醋酸介质中电 催化还原质子制氢的应用，其电催化制氢活性测试步骤如下：
1)将3.3mg(CH3O(CH2)3N(PPh2)2)Ni(mnt)(0.005mmol)放置于电解槽中，加 入5mL支持电解质溶液(0.1mol/L n-Bu4NPF6/CH3CN)。待完全溶解后，将直 径3mm的玻碳电极(工作电极)、铂丝电极(辅助电极)和银丝电极(参比电 极)放置于电解槽中，连接好三电极，打开测试软件，检查电化学工作站；
2)向溶液中通入氮气赶走空气，设置好电化学工作站参数，在室温下测 试单核配合物的循环伏安；
3)在上述测试后的溶液中分别加入2mmol、4mmol、6mmol、8mmol和 10mmol醋酸后，再分别测试单核配合物的循环伏安，其测试结果见图4所 示。
由图4可知，本发明的单核镍配合物(CH3O(CH2)3N(PPh2)2)Ni(mnt)在醋酸介 质中具有良好的电催化还原质子制氢的活性。
实施例7：
本实施例提供了单核镍配合物(CH3O(CH2)3N(PPh2)2)Ni(mnt)在三氟乙酸介 质中电催化还原质子制氢的应用，其电催化制氢活性测试步骤如下：
1)将3.3mg(CH3O(CH2)3N(PPh2)2)Ni(mnt)(0.005mmol)放置于电解槽中，加 入5mL(0.1mol/mL n-Bu4NPF6/CH3CN)支持电解质溶液。将直径3mm的玻碳 电极(工作电极)、铂丝电极(辅助电极)和银丝电极(参比电极)放置入电 解槽中，连接好三电极，打开测试软件，检查电化学工作站；
2)向溶液中通入氮气赶走空气，设置好电化学工作站参数，在室温下测 试单核配合物的循环伏安；
3)在上述测试后的溶液中分别加入5mmol、10mmol、15mmol、20mmol和 25mmol三氟乙酸后，再分别测试单核配合物的循环伏安，其测试结果见图5 所示。
由图5可知，本发明的单核镍配合物(CH3O(CH2)3N(PPh2)2)Ni(mnt)在三氟乙 酸介质中具有高效的电催化还原质子制氢的活性。
实施例8：
本实施例提供了单核镍配合物(CH3O(CH2)3N(PPh2)2)Ni(mnt)在对甲苯磺酸介 质中电催化还原质子制氢的应用，其电催化制氢活性测试步骤如下：
1)将3.3mg(CH3O(CH2)3N(PPh2)2)Ni(mnt)(0.005mmol)放置于电解槽中， 加入5mL(0.1mol/mL n-Bu4NPF6/CH3CN)支持电解质溶液，将直径3mm的玻 碳电极(工作电极)、铂丝电极(辅助电极)和银丝电极(参比电极)放置入 电解槽中，连接好三电极，打开测试软件，检查电化学工作站；
2)向溶液中通入氮气赶走空气，设置好电化学工作站参数，在室温下测 试单核配合物的循环伏安；
3)在上述测试后的溶液中分别加入含2mmol、4mmol、6mmol、8mmol和 10mmol对甲苯磺酸的乙腈溶液后，再测试单核配合物的循环伏安，其测试结 果见图6所示。
由图6可知，本发明的单核镍配合物(CH3O(CH2)3N(PPh2)2)Ni(mnt)在对甲 苯磺酸介质中具有高效的电催化还原质子制氢活性。
以上所述实例仅是本专利的优选实施方式，但本专利的保护范围并不局限 于此。应当指出，对于本技术领域的普通技术人员来说，在不脱离本专利原理 的前提下，根据本专利的技术方案及其专利构思，还可以做出若干改进和润 饰，这些改进和润饰也应视为本专利的保护范围。
Claims (2)
1.一种含N-取代双(二苯基膦基)氨和马来腈二硫醇盐配体的单核镍配合物，其特征在于：该单核镍配合物由R-PNP、马来腈二硫醇盐配体与金属镍原子连接而成，其化学结构如下:
其中，R为3-甲氧基丙基、3-甲硫基丙基、1-苯乙基、异戊基或对甲苯基；该单核镍配合物作为电催化制氢催化剂，电催化制氢的酸性介质为醋酸、三氟乙酸或对甲苯磺酸。
2.如权利要求1所述单核镍配合物的合成方法，其特征在于包括以下步骤:1)将R-N(PPh2)2NiCl2和Na2mnt与有机溶剂混合，在20-40℃下搅拌反应1-3小时，得橙红色溶液；2)采用旋转蒸发仪减压除去溶剂，用二氯甲烷溶解，以二氯甲烷和甲醇的混合溶剂作展开剂进行薄层色谱分离，收集橙红色带，洗脱后得橙红色的单核镍配合物；所述的有机溶剂为三氯甲烷或二氯甲烷，R-N(PPh2)2NiCl2、Na2mnt和有机溶剂的用量比为:1mmol:1mmol:20-30mL；所述的展开剂为二氯甲烷和甲醇的体积比例为10:1-20:1或1:0，薄层色谱分离所需硅胶板的规格为26×20×0.25cm3。
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