CN108484685B - 一种单核镍配合物作为电催化制氢和光催化降解有机染料催化剂的应用 - Google Patents
一种单核镍配合物作为电催化制氢和光催化降解有机染料催化剂的应用 Download PDFInfo
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- CN108484685B CN108484685B CN201810237784.8A CN201810237784A CN108484685B CN 108484685 B CN108484685 B CN 108484685B CN 201810237784 A CN201810237784 A CN 201810237784A CN 108484685 B CN108484685 B CN 108484685B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 37
- 239000001257 hydrogen Substances 0.000 title claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 title description 5
- 239000003446 ligand Substances 0.000 claims abstract description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000002815 nickel Chemical class 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 13
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 N-substituted diphosphino ammonia Chemical class 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- DKAXSGWOJGVZGP-UHFFFAOYSA-N 3h-dithiole-3-carboxylic acid Chemical compound OC(=O)C1SSC=C1 DKAXSGWOJGVZGP-UHFFFAOYSA-N 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 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 18
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 16
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 claims description 11
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 11
- 229940043267 rhodamine b Drugs 0.000 claims description 11
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 3
- 229940012189 methyl orange Drugs 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- LDKSCZJUIURGMW-UHFFFAOYSA-N 1-isothiocyanato-3-methylsulfanylpropane Chemical group CSCCCN=C=S LDKSCZJUIURGMW-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000975 dye Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 abstract description 13
- 238000001308 synthesis method Methods 0.000 abstract description 10
- 238000011161 development Methods 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 61
- 239000000243 solution Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 13
- 238000002484 cyclic voltammetry Methods 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 8
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical class PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000004809 thin layer chromatography Methods 0.000 description 8
- 108010020056 Hydrogenase Proteins 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 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 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 3
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 3
- 235000010703 Modiola caroliniana Nutrition 0.000 description 3
- 244000038561 Modiola caroliniana Species 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 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
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent 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
- QSLPNSWXUQHVLP-UHFFFAOYSA-N $l^{1}-sulfanylmethane Chemical compound [S]C QSLPNSWXUQHVLP-UHFFFAOYSA-N 0.000 description 2
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 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 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- NIAAGQAEVGMHPM-UHFFFAOYSA-N 4-methylbenzene-1,2-dithiol Chemical compound CC1=CC=C(S)C(S)=C1 NIAAGQAEVGMHPM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 description 1
- YQMDBOZKFVFKPJ-UHFFFAOYSA-N azaphosphinine Chemical class C1=CC=PN=C1 YQMDBOZKFVFKPJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
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- 150000007944 thiolates Chemical class 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
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Abstract
本发明涉及氢能源开发和环境保护领域，具体为一种具有电催化制氢和光催化降解有机染料性能的含N‑取代双膦氨和1,2‑二硫酚盐配体的的单核镍配合物，该配合物是由R‑PNP和1,2‑苯二硫酚盐(bdt)(或4‑甲基‑1,2‑苯二硫酚盐(bdtMe))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，并对有机染料具有高效的光催化降解作用。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，适合于具有催化制氢性能和光催化降解有机染料活性的系列含N‑取代双膦氨和取代‑1,2‑苯二硫酚盐配体的单核镍配合物的合成，在氢能源开发和环境保护领域有潜在的应用价值。
Description
技术领域
本发明涉及氢能源开发和环境保护领域，具体为一种由N-取代双膦氨(R-PNP)和1,2-苯二硫酚盐(bdt)(或4-甲基-1,2-苯二硫酚盐(bdtMe))配体与金属镍原子连接而成的一种单核镍配合物作为电催化制氢催化剂和光催化降解有机染料催化剂的应用。
背景技术
随着社会经济的高速发展，不仅能源危机变得日益突出，而且环境污染问题也越发严峻，因此开发一种同时具有高效制氢活性和降解有机染料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能源绝大多数为不可再生的、且常常具有一定污染性。而氢能源具有燃烧热值高和无污染的特点，因此氢能源的开发格外受到各国政府的高度重视。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。而氢化酶作为微生物体内一种能够高效催化氢气氧化和质子还原的金属蛋白酶，氢化酶分为[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，是氢能源开发的重要途径之一。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)、二元胺(N∩N)或氮膦(N∩P)化合物等)和二硫醇盐配体(Hao P.,Song S.,Xiao T.,et al.Polyhedron,2013,52,1138-1144；Dyer P.W.,Fawcett J.,Hanton M.J.Organometallics,2008,27,5082-5087；GuanZ.,Marshall W.J.Organometallics,2002,21,3580-3586)。其中，N-取代双膦氨(R-PNP)是一类新颖的螯合膦配体，通过引入硫醇盐或二硫醇盐配体，可用于氢化酶模型物的合成(Liu X.F.,Li X.,Yan J.Polyhedron,2015,85,482-487；Liu X.F.Inorg.Chim.Acta.,2014,421,10-17；Song L.C.,Li J.P.,Xie Z.J.,et al.Inorg.Chem.,2013,52,19,11618-26)，但这些金属配合物的催化制氢性能研究相对较少，或者有些配合物没有有制氢活性，例如含dppe(1,2-双(二苯基膦)乙烷)和bdt配体的单核镍配合物(dppe)Ni(bdt)无论是在弱酸醋酸还是在强酸对甲苯磺酸介质中均没有电催化制氢活性(Gan L.,Groy T.L.,Tarakeshwar P.,et al,J.Am.Chem.Soc.,2015,137,1109-1115)。
已有的一些研究表明：单核镍配合物表现出一定的光催化降解有机染料活性(WuY.,Lu L.,Feng J.S.,et al.J.Solid State Chem.,2017,254,213-218；Meng X.M.,WangY.L.,Zhang X.,et al.Inorg.Chem.Commun.2016,73,98-102)。但是与其电催化制氢研究相比，单核镍配合物的光催化研究相对更少，而且目前还没有人把配合物的催化制氢和降解有机染料活性结合起来开展研究。
因此开发出一类具有电催化制氢性能和降解有机染料活性的合成方法简便、反应条件温和的单核金属配合物对缓解日益严重的能源危机和环境污染治理具有重要的现实意义。
发明内容
本发明目的在于根据以上技术问题，提供一种含新颖配体N-取代双膦氨和1,2-苯二硫酚盐(或4-甲基-1,2-苯二硫酚盐)的单核镍配合物(R-PNPNi(bdt)和R-PNPNi(bdtMe))，该配合物具有高效的电催化制氢活性和光催化降解有机染料活性，在氢能源开发和环境保护领域有潜在的工业应用价值。其电催化制氢的酸性介质为醋酸、三氟乙酸或对甲苯磺酸；用于光催化降解的有机染料为罗丹明B、甲基紫或甲基橙。
本发明的另外一个目的是提供以上所述化合物的合成方法，该合成方法简便、产率高。
本发明目的通过下述技术方案来实现：
一种含N-取代双膦氨(R-PNP)和1,2-二硫酚盐配体的单核镍配合物，它是由N-取代双膦氨和1,2-苯二硫酚盐(bdt)(或4-甲基-1,2-苯二硫酚盐)配体与金属镍原子连接而成的一种单核镍属配合物，其化学结构式如下：
其合成方法为：
1)将R-N(PPh2)2NiCl2、H2bdt(或H2bdtMe)、三乙胺与有机溶剂混合，在20-40℃下搅拌反应1-3小时，得紫红色溶液；
2)采用旋转蒸发仪减压去除溶剂，用二氯甲烷溶解，以二氯甲烷和石油醚的混合溶剂作展开剂进行薄层色谱分离，收集紫红色带，洗脱后得紫红色的单核镍配合物。
作为优选，所述有机溶剂为三氯甲烷或二氯甲烷，R-N(PPh2)2NiCl2、H2bdt(或H2bdtMe)、三乙胺与有机溶剂的用量比为：1mmol:1mmol:2mmol:20-30mL。
所述展开剂二氯甲烷和石油醚的体积比为2：1-1：0，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：
本发明具有以下有益效果：
(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bdt(或取代bdt)配体的单核镍配合物的合成。
(三)本发明的单核镍配合物，不仅在醋酸、三氟乙酸、对甲苯磺酸等酸性介质中具有电催化还原质子制氢的性能，而且还对罗丹明B、甲基紫、甲基橙等有机染料具有光催化降解性能，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(bdt)的核磁共振氢谱；
图2为实施例1中的(CH3O(CH2)3N(PPh2)2)Ni(bdt)的核磁共振碳谱；
图3为实施例1中的(CH3O(CH2)3N(PPh2)2)Ni(bdt)的核磁共振磷谱；
图4为实施例7中的(CH3O(CH2)3N(PPh2)2)Ni(bdt)在醋酸中的循环伏安图；
图5为实施例8中的(CH3O(CH2)3N(PPh2)2)Ni(bdt)在三氟乙酸中的循环伏安图；
图6为实施例9中的(CH3O(CH2)3N(PPh2)2)Ni(bdt)在对甲苯磺酸中的循环伏安图；
图7为实施例10中的(CH3O(CH2)3N(PPh2)2)Ni(bdt)对罗丹明B降解的混合液随光照时间的紫外-可见光谱图；
图8为实施例11中的(CH3O(CH2)3N(PPh2)2)Ni(bdt)对甲基紫降解的混合液随光照时间的紫外-可见光谱图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
本说明书中公开的所有特征，或公开的所有方法或过程中的步骤，除了互相排斥的特征和/或步骤以外，均可以以任何方式组合。本说明书中公开的任一特征，除非特别叙述，均可被其他等效果或具有类似目的替代特征加以替换，即，除非特别叙述，每个特征只是一系列等效或类似特征中的一个例子而已。
实施例1：
一种含N-取代双膦氨和1,2-苯二硫酚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(bdt)，其合成反应如下：
所述的含N-取代双膦氨和1,2-苯二硫酚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0.0711g H2bdt(0.5mmol)、0.2925g(CH3O(CH2)3N(PPh2)2)NiCl2(0.5mmol)和20mL二氯甲烷混合，在室温下搅拌反应3小时，得紫红色溶液。旋转蒸发仪减压去除溶剂，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，收集红色带，洗脱后得0.2922g，产率89.2％。1H NMR(400MHz,CDCl3):1.325-1.366(m,2H,CH2),2.925(t,J＝5.80Hz,2H,NCH2),3.053(s,3H,CH3O),3.036-3.137(m,2H,OCH2),6.779-6.802(q,J＝2.80Hz,2H,4-S2C6H4,5-S2C6H4),7.409-7.432(q,J＝3.20Hz,2H,3-S2C6H4,6-S2C6H4),7.507(t,J＝7.20Hz,8H,Ph),7.583(t,J＝7.20Hz,4H,Ph),7894-7.946(m,8H,Ph)ppm.13C NMR(100.6MHz,CDCl3):29.746(CH2),45.914(t,2JCP＝7.85Hz,NCH2),58.468(CH3),69.438(OCH2),121.201(4-S2C6H4,5-S2C6H4),127.601(3-S2C6H4,6-S2C6H4),129.065(t,3JCP＝5.58Hz,m-Ph),130.398,130.326.130.554(p-Ph),132.202(1-S2C6H4,2-S2C6H4),133.064(t,2J CP＝6.24Hz,o-Ph),147.946(t,1JCP＝10.21Hz,i-Ph)ppm.31P NMR(161.9MHz,CDCl3,85％H3PO4):62.731(s,2P,NP2)ppm。其核磁共振谱图见图1-图3所示。
实施例2：
一种含N-取代双膦氨和1,2-苯二硫酚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(bdt)，其化学结构式如下：
所述的含N-取代双膦氨和1,2-苯二硫酚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0.0711g H2bdt(0.5mmol)、0.3005g(CH3S(CH2)3N(PPh2)2)NiCl2(0.5mmol)和20mL二氯甲烷混合，在室温下搅拌反应3小时，得紫红色溶液。旋转蒸发仪减压去除溶剂，用适量二氯甲烷溶解，以2:1的二氯甲烷和石油醚混合液作展开剂进行薄层色谱分离，收集红色带，洗脱后得0.2876g，产率85.7％。
实施例3：
一种含N-取代双膦氨和1,2-苯二硫酚盐配体的单核镍配合物，所述单核镍配合物的化学式为(CH3CH(Ph)N(PPh2)2)Ni(bdt)，其化学结构式如下：
所述的含N-取代双膦氨和1,2-苯二硫酚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0.0711g H2bdt(0.5mmol)、0.3090g(CH3CH(Ph)N(PPh2)2)NiCl2(0.5mmol)和20mL三氯甲烷混合，在室温下搅拌反应2小时，得紫红色溶液。旋转蒸发仪减压去除溶剂，用适量三氯甲烷溶解，以3:1的二氯甲烷和石油醚混合液作展开剂进行薄层色谱分离，收集红色带，洗脱后得0.2606g，产率75.9％。
实施例4：
一种含N-取代双膦氨和4-甲基-1,2-苯二硫酚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(bdtMe)，其化学结构式如下：
所述的含N-取代双膦氨和4-甲基-1,2-苯二硫酚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0.0832g H2bdtMe(0.5mmol)、0.2925g(CH3O(CH2)3N(PPh2)2)NiCl2(0.5mmol)和20mL二氯甲烷混合，在室温下搅拌反应3小时，得紫红色溶液。旋转蒸发仪减压去除溶剂，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，收集红色带，洗脱后得0.2796g，产率83.6％。
实施例5：
一种含N-取代双膦氨和4-甲基-1,2-苯二硫酚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(bdtMe)，其化学结构式如下：
所述的含N-取代双膦氨和4-甲基-1,2-苯二硫酚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0.0832g H2bdtMe(0.5mmol)、0.3005g(CH3S(CH2)3N(PPh2)2)NiCl2(0.5mmol)和20mL二氯甲烷混合，在室温下搅拌反应3小时，得紫红色溶液。旋转蒸发仪减压去除溶剂，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，收集红色带，洗脱后得0.2986g，产率87.2％。
实施例6：
一种含N-取代双膦氨和4-甲基-1,2-苯二硫酚盐配体的单核镍配合物，所述单核镍配合物的化学式为(CH3CH(Ph)N(PPh2)2)Ni(bdtMe)，其化学结构式如下：
所述的含N-取代双膦氨和4-甲基-1,2-苯二硫酚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0.0832g H2bdtMe(0.5mmol)、0.3090g(CH3CH(Ph)N(PPh2)2)NiCl2(0.5mmol)和20mL三氯甲烷混合，在室温下搅拌反应3小时，得紫红色溶液。旋转蒸发仪减压去除溶剂，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，收集红色带，洗脱后得0.2491g，产率71.0％。
实施例7：
本实施例提供了单核镍配合物(CH3O(CH2)3N(PPh2)2)Ni(bdt)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3.4mg(CH3O(CH2)3N(PPh2)2)Ni(bdt)(0.005mmol)放置于电解槽中，加入5mL支持电解质溶液(0.1mol/L n-Bu4NPF6/DCM)。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，再测试该单核配合物在醋酸介质中的循环伏安，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(bdt)在醋酸介质中能高效的电催化还原质子制氢活性。
实施例8：
本实施例提供了单核镍配合物(CH3O(CH2)3N(PPh2)2)Ni(bdt)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3.4mg(CH3O(CH2)3N(PPh2)2)Ni(bdt)(0.005mmol)放置于电解槽中，加入5mL(0.1mol/mL n-Bu4NPF6/DCM)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2mmol、4mmol、6mmol、8mmol和10mmol三氟乙酸，再测试该单核配合物在三氟乙酸介质中的循环伏安，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(bdt)在三氟乙酸介质中能高效的电催化还原质子制氢活性。
实施例9：
本实施例提供了单核镍配合物(CH3O(CH2)3N(PPh2)2)Ni(bdt)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3.4mg(CH3O(CH2)3N(PPh2)2)Ni(bdt)(0.005mmol)放置于电解槽中，加入5mL(0.1mol/mL n-Bu4NPF6/DCM)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，再测试该单核配合物在对甲苯磺酸介质中的循环伏安，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(bdt)在对甲苯磺酸介质中能高效的电催化还原质子制氢活性。
实施例10：
本实施例提供了单核镍配合物(CH3O(CH2)3N(PPh2)2)Ni(bdt)光催化降解罗丹明B的应用，其催化降解罗丹明B活性测试步骤如下：
1)将50mg(CH3O(CH2)3N(PPh2)2)Ni(bdt)置于光催化反应器中，将50mL浓度为5mg/L的罗丹明B水溶液注入其中，开启搅拌器，在避光环境下搅拌30min，确保该单核配合物对罗丹明B染料的吸附/脱附达到平衡状态。
2)开启250W高压汞灯，在室温下每隔5min取出5mL罗丹明B溶液，离心后通过紫外-可见分光光度计记录溶液的紫外-可见吸收光谱，其紫外-可见吸收光谱图随时间的变化见图7所示，罗丹明B的降解率见表1。
表1(CH3O(CH2)3N(PPh2)2)Ni(bdt)对罗丹明B的降解率与时间的关系
由图7和表1可知，单核镍配合物(CH3O(CH2)3N(PPh2)2)Ni(bdt)在紫外光照射下，可有效催化罗丹明B的降解反应，在45min时的降解率为74.64％。
实施例11：
本实施例提供单核镍配合物(CH3O(CH2)3N(PPh2)2)Ni(bdt)光催化降解甲基紫的应用，其催化降解甲基紫活性测试步骤如下：
1)将50mg(CH3O(CH2)3N(PPh2)2)Ni(bdt)置于光催化反应器中，将50mL浓度为5mg/L的甲基紫水溶液注入其中，开启搅拌器，在避光环境下搅拌30min，确保该单核配合物对甲基紫染料的吸附/脱附达到平衡状态。
2)开启250W高压汞灯，在室温下每隔5min取出5mL甲基紫溶液，离心后通过紫外-可见分光光度计记录溶液的紫外-可见吸收光谱，其紫外-可见吸收光谱图随时间的变化见图8所示，甲基紫的降解率见表2。
表2(CH3O(CH2)3N(PPh2)2)Ni(bdt)对甲基紫的降解率与时间的关系
由图8和表2可知，单核镍配合物(CH3O(CH2)3N(PPh2)2)Ni(bdt)在紫外光照射下，可有效催化甲基紫染料的降解，在45min时的降解率为82.82％。
本发明所述的技术方案目前还未见相关文献公开报道。以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (2)
1.一种含N-取代双膦氨和1,2-二硫酚盐配体的单核镍配合物，其特征在于:它是由R-PNP和1,2-苯二硫酚盐或4-甲基-1,2-苯二硫酚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:
其中，R1为氢原子或甲基，R2为3-甲氧基丙基或3-甲硫基丙基。
2.如权利要求1所述的单核镍配合物，其特征在于，该配合物为:
其中，R1为氢原子，R2为3-甲氧基丙基，该单核镍配合物具有电催化制氢和光催化降解有机染料性能；有机染料为罗丹明B、甲基紫或甲基橙；电催化制氢的酸性介质为醋酸、三氟乙酸或对甲苯磺酸。
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