CN105884745B - 镍-卡宾双核配合物及其制备方法和应用 - Google Patents
镍-卡宾双核配合物及其制备方法和应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 57
- 150000001450 anions Chemical class 0.000 claims abstract description 20
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 60
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
- -1 halogen Anion Chemical class 0.000 claims description 20
- 239000003446 ligand Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 15
- 238000006722 reduction reaction Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000001699 photocatalysis Effects 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 4
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- BBHXYKROLWOEKT-UHFFFAOYSA-N 1,2,4,5-tetrabromo-3-methylbenzene Chemical class CC1=C(Br)C(Br)=CC(Br)=C1Br BBHXYKROLWOEKT-UHFFFAOYSA-N 0.000 claims description 3
- GHSYRZLWQQWDEF-UHFFFAOYSA-N 3,5-dibromo-4-methyl-1h-pyrazole Chemical compound CC=1C(Br)=NNC=1Br GHSYRZLWQQWDEF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003504 photosensitizing agent Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000003115 supporting electrolyte Substances 0.000 claims description 3
- 150000005360 2-phenylpyridines Chemical class 0.000 claims description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 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 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- HGJLYMGBCAKBLK-UHFFFAOYSA-N sodium;trifluoromethanesulfonic acid Chemical compound [Na].OS(=O)(=O)C(F)(F)F HGJLYMGBCAKBLK-UHFFFAOYSA-N 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XKVUYEYANWFIJX-UHFFFAOYSA-N 5-methyl-1h-pyrazole Chemical compound CC1=CC=NN1 XKVUYEYANWFIJX-UHFFFAOYSA-N 0.000 description 1
- 229910017673 NH4PF6 Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- 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
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
- B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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Abstract
本发明公开一类镍‑卡宾双核配合物,其具有如下分子结构式I或II:其中:X‑表示平衡电荷的一价阴离子。本发明还公开了该镍‑卡宾双核配合物的制备方法,该制备过程简单,制备成本低。本发明还公开了该镍‑卡宾双核配合物在催化还原CO2中的应用。
Description
技术领域
本发明涉及能源和催化领域。更具体地,涉及一种镍-卡宾双核配合物及其制备方法和应用。
背景技术
随着社会的进步,经济的发展,人类对化石能源的需求日益增加,不可再生的化石燃料大量燃烧也造成了日益严重的能源及环境问题。CO2是温室气体的主要成分之一,它含量的上升会导致全球变暖等一系列问题,将温室气体CO2转化为CO,CH4等燃料,既能解决环境问题,又能创造新的能源,因此,将CO2催化还原为燃料成为能源研究领域的热点。
目前,CO2还原转换方法已有大量文献报导(Chem.Rev.2007,107,2365-2387),主要有催化加氢、催化重整反应、光化学转化、电化学转化等。其中催化加氢、催化重整等通常在高温高压下进行,对能量的供给、设备的强度等均有较高要求。而光化学和电化学转化分别利用可再生的电能和太阳能,在温和的条件下进行反应,是较为理想的途径。
作为氧化程度最高的含C化合物,CO2有非常高的稳定性,将其直接还原为单电子自由基CO2·-需要很高的还原电势(-1.9V vs.NHE),而通过质子偶合的多电子还原过程能显著降低还原电势(Coord.Chem.Rev.1999,185–186,373-384.),目前,能够实现多电子还原过程的催化剂以铼、钌等贵金属配合物居多,发展更具实用性的非贵金属催化剂是目前CO2还原中的重要目标(Chem.Soc.Rev.2012,41,2036;Chem.Rev.2013,113,6621),目前的非贵金属催化剂主要有Ni,Co的四氮杂环配合物以及Fe,Co的卟啉配合物等。但这些非贵金属催化剂的催化效果并不理想,如Fe卟啉配合物催化剂只能维持50h的催化活性(J.AmChem.Soc.,2014,136,16768-16771),最高催化转换数(TON)只有几百,离实际应用有很大的距离。镍-卡宾单核配合物催化剂具有很高的催化活性,其最高催化转换数可以达到98000(J.Am.Chem.Soc.2013,135,14413-14424),这和催化还原CO2的实际应用(TON~100万)所要求的差距已经显著缩小了,发展镍-卡宾配合物催化剂具有很好的应用前景。
双核金属配合物在超分子光化学及电化学中有重要地位,由于具有两个金属中心,可以更好的满足多电子还原过程中电子转移,最近的研究也进一步表明,双核金属配合物在催化还原CO2方面可以表现出良好的协同效应(Dalton Trans.,2014,43,13259–13269),本发明提供一系列镍-卡宾双核配合物催化剂及其制备方法,同时提供镍-卡宾双核配合物作为催化剂在催化还原CO2中的应用。
发明内容
本发明的第一个目的在于提供一种镍-卡宾双核配合物,该配合物有两个Ni配位中心,且在水和空气中具有良好的稳定性,易于存储。
本发明的第二个目的在于提供镍-卡宾双核配合物的制备方法,该制备方法简单,易于大量制备,且镍为非贵金属,配合物的合成及使用成本均很低。
本发明的第三个目的在于提供镍-卡宾双核配合物在催化还原CO2中的应用。
为达到上述第一个目的,本发明采用下述技术方案:
一种镍-卡宾双核配合物,具有如下分子结构式I或II:
其中:X-表示平衡电荷的一价阴离子;Ⅱ中Ni------Ni表示两个金属中心之间的相互作用。
所述一价阴离子选自卤素阴离子、对甲苯磺酸根(OTs-)、三氟甲磺酸根(OTf-)、四氟硼酸根(BF4 -)、六氟磷酸根(PF6 -)或双三氟甲磺酸取代氨基阴离子(NTf2 -)中的一种;所述卤素阴离子选自F-、Cl-、Br-或I-。
为达到上述第二个目的,本发明采用下述技术方案:
本发明保护上述镍-卡宾双核配合物的制备方法,具体的,
当镍-卡宾双核配合物的分子结构式为I时,镍-卡宾双核配合物的制备包括如下步骤:
1)在N2气氛下,将3-(1H-咪唑-1-基)异喹啉和1,2,4,5-四溴甲基苯以摩尔比1:4的比例混合,并溶于DMSO溶液中,加热至70~80℃,反应12~16h,过滤,得到固体,并将固体溶于水中,加入8~10摩尔当量的NH4PF6,得到配体;
2)在N2气氛下,将步骤1)所得配体与Ag2O以摩尔比1:4~8混合,并溶于乙腈中,在室温下搅拌反应24h,过滤,收集滤液,向滤液中加入2摩尔当量的Ni(DME)Cl2固体,常温搅拌反应24h,过滤,收集并浓缩滤液,用乙醚沉淀,得到镍-卡宾双核配合物主体;
3)将步骤2)所得镍-卡宾双核配合物主体溶于乙腈中,在常温下与8~10摩尔当量的阴离子钠盐搅拌反应24h,得到镍-卡宾双核配合物。
当镍-卡宾双核配合物的分子结构式为II时,镍-卡宾双核配合物的制备包括如下步骤:
(1)在N2气氛下,将3-(1H-咪唑-1-基)异喹啉和3,5-二溴甲基吡唑以摩尔比1:2的比例混合,并溶于丙酮溶液中,加热至70~80℃,反应12~16h,过滤,得到固体,并将固体溶于水中,加入4~6摩尔当量NH4PF6,得到配体;
(2)在N2气氛下,将步骤(1)所得配体与Ag2O以摩尔比1:4~8混合,并溶于乙腈中,在室温下搅拌反应24h,过滤,收集滤液,向滤液中加入2摩尔当量的Ni(DME)Cl2固体,常温搅拌反应24h,过滤,收集并浓缩滤液,用乙醚沉淀,得到镍-卡宾双核配合物主体;
(3)将步骤(2)所得镍-卡宾双核配合物主体溶于乙腈中,在常温下与4~6摩尔当量的阴离子钠盐搅拌反应24h,得到镍-卡宾双核配合物。
所述阴离子钠盐选自氟化钠、氯化钠、溴化钠、碘化钠、对甲苯磺酸钠、三氟甲磺酸钠、四氟硼酸钠、六氟磷酸钠或双三氟甲磺酸氨基钠中的一种。
上述制备方法中,所述3-(1H-咪唑-1-基)异喹啉根据文献“J.Am.Chem.Soc.2013,135,14413-14424”中的方法制备得到;所述Ni(DME)Cl2根据文献“Organometallics 2008,27,88–99”中的方法制备得到;所述3,5-二溴甲基吡唑根据文献“Organometallics 2008,27,5911–5920”中的方法制备得到,其余原料均可通过市售购买获得。
为达到上述第三个目的,本发明提供上述镍-卡宾双核配合物在催化还原CO2中的应用。
进一步地,保护所述镍-卡宾双核配合物作为催化剂在光催化或电催化还原CO2体系中的应用。
本发明提供镍-卡宾双核配合物作为催化剂,用于光催化还原CO2的催化体系:以镍-卡宾双核配合物作为光催化剂,以三(2-苯基吡啶)合铱配合物为光敏剂,以三乙胺为牺牲体,在乙腈溶剂中构建而成。
本发明提供镍-卡宾双核配合物作为催化剂,用于电催化还原CO2的催化体系:以镍-卡宾双核配合物作为催化剂,NBu4PF6为支持电解质,在乙腈溶剂中构建而成。
本发明的有益效果如下:
镍-卡宾双核配合物合成过程简单,易于大量制备,该配合物有良好的稳定性,方便储存;镍为非贵金属,镍-卡宾双核配合物合成和使用的成本低,便于应用;结构I和II中的利用3-(1H-咪唑-1-基)异喹啉配位结构,形成的配合物还原电位和CO2还原电位相匹配,从而有利于CO2还原;同时,双核配合物具有两个金属中心,在CO2还原中具有协同作用,有利于提高催化剂的催化活性和催化效果。本发明制备的镍-卡宾双核配合物可以作为光催化剂和电催化剂用于CO2还原体系,表现出显著的催化活性。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明。
图1示出实施例1所得镍-卡宾双核配合物配体的核磁氢谱(400M Hz,CD3CN)。
图2示出实施例2所得镍-卡宾双核配合物主体的核磁氢谱(400M Hz,CD3CN)。
图3示出实施例5制备得到镍-卡宾双核配合物的核磁氢谱(400M Hz,CD3CN)。
图4示出实施例8制备得到镍-卡宾双核配合物的核磁氢谱(400M Hz,CD3CN)。
具体实施方式
为了更清楚地说明本发明,下面结合优选实施例和附图对本发明做进一步的说明。附图中相似的部件以相同的附图标记进行表示。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。
实施例1
镍-卡宾双核配合物的配体制备,反应路线如下:
在N2保护下,将3-(1H-咪唑-1-基)异喹啉和1,2,4,5-四溴甲基苯以摩尔比1:4的比例混合,在DMSO溶液下,加热至70℃~80℃,反应16h,混合液过滤得到固体,并溶于水中,加入10摩尔当量的NH4PF6,得到相应的配体结构。配体的核磁氢谱如图1所示,核磁表征数据如下:1H NMR(400MHz,CD3CN)δ9.40(s,1H),9.08(s,1H),8.19(s,1H),8.06(d,J=8.8Hz,2H),7.87(d,J=8.1Hz,1H),7.82(t,J=7.3Hz,1H),7.74(t,J=7.4Hz,1H),7.59(s,1H),7.35(s,1H),5.68(s,2H).
实施例2
镍-卡宾双核配合物的配体制备,反应路线如下:
在N2保护下,将3-(1H-咪唑-1-基)异喹啉和3,5二溴甲基吡唑以摩尔比1:2的比例混合,在丙酮溶液下,加热至70℃~80℃,反应12h,混合液过滤得到固体,并溶于水中,加入6摩尔当量的NH4PF6,得到相应的配体结构。化合物Ni-Ni配体的核磁氢谱如图2所示,核磁表征数据如下:1H NMR(400MHz,CD3CN)δ11.59(s,1H),9.48(s,2H),9.30(d,J=7.5Hz,2H),8.29–8.16(m,6H),8.08(d,J=8.2Hz,2H),7.94(t,J=7.5Hz,2H),7.83(t,J=7.5Hz,2H),7.66(s,2H),6.70(s,1H),5.56(s,4H).
实施例3
镍-卡宾双核配合物I主体结构的制备,反应路线如下:
将1当量的实施例1制备得到的配体溶于乙腈中,加入8摩尔当量的Ag2O固体,室温下搅拌反应24h;减压除去固体,向滤液中加入2摩尔当量的Ni(DME)Cl2固体室温下反应24h;减压除去固体,将得到的溶液浓缩,用乙醚沉淀,得到镍-卡宾双核配合物Ni-ph-Ni的主体结构Ni-ph-Ni·Clx(PF6)y,其中x+y=4,x为0、1、2、3或4。
实施例4
镍-卡宾双核配合物II主体结构的制备,反应路线如下:
将1当量的实施例2制备得到的配体溶于乙腈中,加入4摩尔当量的Ag2O固体,室温下搅拌反应24h;减压除去固体,向得到的溶液中刚加入2摩尔当量的Ni(DME)Cl2固体室温下反应24h;减压除去固体,将得到的溶液浓缩,用乙醚沉淀,得到镍-卡宾双核配合物Ni–Ni的主体结构Ni-Ni·Clx(PF6)y,其中x+y=2,x为0、1或2。
实施例5
以PF6 -为阴离子的镍-卡宾双核配合物I(Ni-ph-Ni)的制备:
将实施例3中得到的镍-卡宾双核配合物主体结构溶于乙腈中,加入10摩尔当量的NaPF6固体,在常温下搅拌24h,过滤除去固体,滤液浓缩,加入乙醚沉淀得到以PF6 -为阴离子的镍-卡宾双核配合物。配合物核磁氢谱如图3所示,核磁表征数据如下:1H NMR(400MHz,CD3CN)δ9.42(s,2H),8.31(d,J=4.7Hz,4H),8.18–8.09(m,4H),8.04(t,J=7.6Hz,2H),7.86(t,J=7.6Hz,2H),7.79(d,J=4.1Hz,1H),7.44(d,J=1.9Hz,1H),7.35(d,J=1.8Hz,1H),5.16(t,J=12.7Hz,4H).
实施例6
以Cl-为阴离子的镍-卡宾双核配合物I(Ni-ph-Ni)制备:
重复实施例5,其不同之处仅在于,加入的阴离子钠盐为NaCl,其余条件不变,得到以Cl-为阴离子的镍-卡宾双核配合物。
实施例7
以OTs-为阴离子的镍-卡宾双核配合物I(Ni-ph-Ni)的制备
重复实施例5,其不同之处仅在于,加入的阴离子钠盐为NaOTs,其余条件不变,得到以OTs-为阴离子的镍-卡宾双核配合物。
实施例8
以PF6 -为阴离子的镍-卡宾双核配合物II(Ni-Ni)的制备:
将镍-卡宾双核配合物Ni-Ni的主体结构溶于乙腈中,加入10摩尔当量的NaPF6固体,在常温下搅拌24h,过滤除去固体,滤液浓缩,加入乙醚沉淀,得到以PF6 -为阴离子的镍-卡宾双核配合物Ni-Ni。配合物核磁氢谱如图4所示,核磁表征数据如下:1H NMR(400MHz,DMSO)δ9.52(s,2H),8.66–8.16(m,6H),7.75(m,8H),6.41(s,1H),5.45(s,4H).
实施例9
以Br-为阴离子的镍-卡宾双核配合物II(Ni-Ni)制备:
重复实施例8,其不同之处仅在于,加入的盐为NaBr,其余条件不变,得到以Br-为阴离子的镍-卡宾双核配合物Ni-Ni。
实施例10
以NTf2 -为阴离子的镍-卡宾双核配合物II(Ni-Ni)制备:
重复实施例8,其不同之处仅在于,加入的盐为NaNTf2,其余条件不变,得到以NTf2 -为阴离子的镍-卡宾双核配合物Ni-Ni。
实施例11
镍-卡宾双核配合物I(Ni-ph-Ni)用于光催化还原CO2:镍-卡宾双核配合物Ni-ph-Ni为催化剂,fac-Ir(ppy)3为光敏剂,TEA为牺牲体,溶剂为乙腈,在CO2氛围下,使用300瓦氙灯为光源,光照该体系,并通过气相色谱检测产生的还原产物CO,具体如下:分别配置不同阴离子的镍-卡宾双核配合物I(Ni-ph-Ni)的乙腈溶液各10mL,配合物浓度为2×10-7M,向其中分别加入2×10-4M的fac-Ir(ppy)3和0.07M的三乙胺(TEA),光照2h后,检测得到CO生成量如表1所示:
表1、不同阴离子的镍-卡宾双核配合物I(Ni-ph-Ni)光催化还原CO2产生的CO量
实施例12
重复实施例11,其不同之处仅在于,加入的催化剂为镍-卡宾双核配合物II(Ni-Ni),其余条件不变,检测得到CO生成量如表2所示:
表2、不同阴离子镍-卡宾双核配合物II光催化还原CO2产生的CO量
实施例13
镍-卡宾双核配合物I(Ni-ph-Ni)用于电催化还原CO2:镍-卡宾双核配合物Ni-ph-Ni为催化剂,乙腈为溶剂,0.1M NBu4PF6为支持电解质,构成电催化还原CO2体系。具体实施如下:分别配置不同阴离子的含镍-卡宾双核配合物Ni-ph-Ni的乙腈溶液10mL,浓度为2×10-3M,固定电压为-1.8V(vs SCE)在CO2氛围下进行电催化还原,电解2h后,检测得到CO生成量如表3所示:
表3、不同阴离子的镍-卡宾双核配合物I(Ni-ph-Ni)电催化还原CO2产生CO量
实施例14
重复实施例13,其不同之处仅在于,加入的催化剂为镍-卡宾双核配合物II(Ni-Ni),其余条件不变,检测得到CO生成量如表4所示:
表4、不同阴离子的镍-卡宾双核配合物II(Ni–Ni)电催化还原产生CO量
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (9)
1.镍-卡宾双核配合物,其特征在于,具有如下分子结构式I或II:
其中:X-表示平衡电荷的一价阴离子;------表示两个金属中心之间的相互作用。
2.根据权利要求1所述的镍-卡宾双核配合物,其特征在于,所述一价阴离子选自卤素阴离子、对甲苯磺酸根、三氟甲磺酸根、四氟硼酸根、六氟磷酸根或双三氟甲磺酸取代氨基阴离子中的一种;所述卤素阴离子选自F-、Cl-、Br-或I-。
3.如权利要求1所述的镍-卡宾双核配合物的制备方法,其特征在于,分子结构式为I的镍-卡宾双核配合物的制备包括如下步骤:
1)在N2气氛下,将3-(1H-咪唑-1-基)异喹啉和1,2,4,5-四溴甲基苯以摩尔比1:4的比例混合,并溶于DMSO溶液中,加热至70~80℃,反应12~16h,过滤,得到固体,并将固体溶于水中,加入8~10摩尔当量的NH4PF6,得到配体;
2)在N2气氛下,将步骤1)所得配体与Ag2O以摩尔比1:4~8混合,并溶于乙腈中,在室温下搅拌反应24h,过滤,收集滤液,向滤液中加入2摩尔当量的Ni(DME)Cl2固体,常温搅拌反应24h,过滤,收集并浓缩滤液,用乙醚沉淀,得到镍-卡宾双核配合物主体;
3)将步骤2)所得镍-卡宾双核配合物主体溶于乙腈中,在常温下与8~10摩尔当量的阴离子钠盐搅拌反应24h,得到镍-卡宾双核配合物。
4.如权利要求1所述的镍-卡宾双核配合物的制备方法,其特征在于,分子结构式为II的镍-卡宾双核配合物的制备包括如下步骤:
(1)在N2气氛下,将3-(1H-咪唑-1-基)异喹啉和3,5-二溴甲基吡唑以摩尔比1:2的比例混合,并溶于丙酮溶液中,加热至70~80℃,反应12~16h,过滤,得到固体,并将固体溶于水中,加入4~6摩尔当量的NH4PF6,得到配体;
(2)在N2气氛下,将步骤(1)所得配体与Ag2O以摩尔比1:4~8混合,并溶于乙腈中,在室温下搅拌反应24h,过滤,收集滤液,向滤液中加入2摩尔当量的Ni(DME)Cl2固体,常温搅拌反应24h,过滤,收集并浓缩滤液,用乙醚沉淀,得到镍-卡宾双核配合物主体;
(3)将步骤(2)所得镍-卡宾双核配合物主体溶于乙腈中,在常温下与4~6摩尔当量的阴离子钠盐搅拌反应24h,得到镍-卡宾双核配合物。
5.根据权利要求3或4所述的镍-卡宾双核配合物的制备方法,其特征在于,所述阴离子钠盐选自氟化钠、氯化钠、溴化钠、碘化钠、对甲苯磺酸钠、三氟甲磺酸钠、四氟硼酸钠、六氟磷酸钠或双三氟甲磺酸氨基钠中的一种。
6.如权利要求1所述的镍-卡宾双核配合物在催化还原CO2中的应用。
7.根据权利要求6所述的应用,其特征在于,所述镍-卡宾双核配合物作为催化剂在光催化或电催化还原CO2体系中的应用。
8.根据权利要求7所述的应用,其特征在于,所述光催化还原CO2体系是指:以镍-卡宾双核配合物作为催化剂,以三(2-苯基吡啶)合铱配合物为光敏剂,以三乙胺为牺牲体,在乙腈溶剂中构建而成。
9.根据权利要求7所述的应用,其特征在于,所述电催化还原CO2体系是指:以镍-卡宾双核配合物作为催化剂,六氟磷酸四丁基铵为支持电解质,在乙腈溶剂中构建而成。
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