CN114478648B - 一种类吡啶吡咯钌配合物及其制备方法和作为电催化氨氧化催化剂的应用 - Google Patents
一种类吡啶吡咯钌配合物及其制备方法和作为电催化氨氧化催化剂的应用 Download PDFInfo
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- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 25
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- -1 pyridine pyrrole ruthenium Chemical compound 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 37
- 239000012327 Ruthenium complex Substances 0.000 claims description 23
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 5
- HWLQJKMTFHIDBF-UHFFFAOYSA-N 2-(5-pyridin-2-yl-1h-pyrrol-2-yl)pyridine Chemical compound C=1C=C(C=2N=CC=CC=2)NC=1C1=CC=CC=N1 HWLQJKMTFHIDBF-UHFFFAOYSA-N 0.000 claims description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 2
- VIBZXIQHXZWZMU-UHFFFAOYSA-N CC=1C(=C(NC=1C1=NC=CC=C1)C1=NC=CC=C1)C(C)=O Chemical compound CC=1C(=C(NC=1C1=NC=CC=C1)C1=NC=CC=C1)C(C)=O VIBZXIQHXZWZMU-UHFFFAOYSA-N 0.000 claims description 2
- VBFDJEQGEJWLPO-UHFFFAOYSA-N N1C=CC=C1.N1=C(C=CC=C1)C=1C=CC=NC1 Chemical compound N1C=CC=C1.N1=C(C=CC=C1)C=1C=CC=NC1 VBFDJEQGEJWLPO-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 25
- 239000001257 hydrogen Substances 0.000 abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 24
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 19
- 230000003647 oxidation Effects 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 239000003446 ligand Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
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- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- AECJYVHHZNOFPN-UHFFFAOYSA-N 1H-pyrrole ruthenium Chemical compound [Ru].c1cc[nH]c1 AECJYVHHZNOFPN-UHFFFAOYSA-N 0.000 description 2
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
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- 150000003384 small molecules Chemical class 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- OFDVABAUFQJWEZ-UHFFFAOYSA-N 3-pyridin-3-ylpyridine Chemical group C1=CN=CC(C=2C=NC=CC=2)=C1 OFDVABAUFQJWEZ-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001028 anti-proliverative effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000004440 column chromatography Methods 0.000 description 1
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- 208000002154 non-small cell lung carcinoma Diseases 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical compound OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 208000029729 tumor suppressor gene on chromosome 11 Diseases 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
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Abstract
本发明公开了一种类吡啶吡咯钌配合物及其制备方法和作为电催化氨氧化催化剂的应用。类吡啶吡咯钌配合物以高活性金属钌为中心金属离子,并以具有较高的给电子能力的类吡啶吡咯化合物作为配体,从而赋予了整个类吡啶吡咯钌配合物较高的氨氧化催化活性,将其用于氨的电催化氧化,可以实现氨的高转化率,并获得氢、氮及肼等为主的产物,具有较高选择性。
Description
技术领域
本发明涉及一种催化材料,具体涉及一种类吡啶吡咯钌配合物催化材料,还涉及其合成方法和作为电催化氨氧化催化剂的应用,属于催化技术领域。
背景技术
氢气(H2)是公认的化石燃料最理想替代品之一,然而,氢气体积能量密度极低、极易燃易爆、储运成本高、安全性差等不利因素限制了氢能的大规模直接使用,因此,储氢技术和储氢材料的发展势在必行。在众多储氢材料中,液态小分子作为氢能载体备受关注。相对于甲醇、甲酸、水等小分子,氨分子(NH3)作为氢能源载体优势明显,但其开发利用一直进展缓慢,主要受制于氨氧化半反应。小分子金属配合物作为均相催化剂为氨分子在温和条件下催化氧化提供了解决方案。
与传统化石燃料将化学能存储于C-C,C-H键中不同,面向氢能源的小分子NH3将化学能存储于O-H和N-H键中(Dunn P L,Cool B J,Johnson S I,et al.Oxidation ofAmmonia with Molecular Complexes[J].Journal of the American Chemical Society,2020,142(42):17845-17858.)。利用其中的氢能,需NH3全分解制备氢气,该分解反应包括NH3氧化半反应和质子还原半反应。很明显,氧化半反应是制约NH3全分解制氢的瓶颈,因为该半反应不仅是一个吸热反应,而且反应过程涉及6e-/6H+转移、不稳定高价态M-NHx(x=0,1or 2)生成、和N-N键的形成,是一个复杂体系反应。
联氨(NH2NH2)作为生产生活中另一个最重要的化学物质,被广泛的应用于有机合成和新能源中。同时,联氨作为氨氧化过程中的重要中间产物已经被广泛的证实。然而在氨氧化过程中直接将NH3转化为NH2NH2是非常困难的,这主要是因为在氧化的过程中NH2NH2中N-N键比NH3中的N-H更容易被氧化从而生成N2。考虑到将NH3为原料直接生产H2和NH2NH2是一种非常经济有效的方法用以解决目前的能源和环境问题。那么在氨氧化过程中要同时具备脱氢和N-N偶联的均相催化剂是有可能会实现这一过程的。而开发一种同时具有较强脱氢能力并且具有较低过电位的均相催化剂成为了目前研究的热点。
发明内容
为了解决现有技术存在的问题,本发明的第一个目的是在于提供一种对电催化氨氧化具有较高活性的类吡啶吡咯金属钌配合物。
本发明的第二个目的是在于提供一种操作和步骤简单、低成本的制备类吡啶吡咯金属钌配合物的方法。
本发明的第三个目的是在于提供了一种类吡啶吡咯钌配合物作为电催化氨氧化催化剂应用,类吡啶吡咯钌配合物对氨的电催化氧化具有较高的活性,能将氨高效转化成氮气和氢气及肼。
为了实现上述技术目的,本发明提供了一种类吡啶吡咯钌配合物,其具有式1~式5结构中任意一种:
本发明的类吡啶吡咯钌配合物是以金属钌为中心金属离子,类吡啶吡咯化合物作为配体,金属钌是属于高周期过渡金属,其具有多种氧化态(其价态范围为-2到+8),表现出较高的反应活性,而类吡啶吡咯配体具有较高的给电子能力,能有效降低氨氧化过电位,同时类吡啶吡咯基团分子内的氢键作用也能够加速氨氧化中脱氢的过程,从而赋予了整个类吡啶吡咯钌配合物较高的氨氧化活性。
本发明还提供了一种类吡啶吡咯钌配合物的合成方法,其包括以下步骤:
1)2,5-二吡啶基吡咯、2,5-二吡啶基-3-甲基-4-乙酰基吡咯或2,5-二吡啶基-3-羧甲基-4-甲基吡咯与顺-二氯四(二甲基亚砜)钌和二联吡啶以及碱性化合物溶于溶剂中,加热回流反应,即得式1、式4或式5结构类吡啶吡咯钌配合物;
2)将式1结构类吡啶吡咯钌配合物溶于溶剂中,先加热回流反应,再加入饱和六氟磷酸铵进行离子交换反应,得到式2结构类吡啶吡咯钌配合物;
3)将式2结构类吡啶吡咯钌配合物溶于溶剂中,再通入含氨气体反应,即得式3结构类吡啶吡咯钌配合物。
作为一个优选的方案,2,5-二吡啶基吡咯、2,5-二吡啶基-3-甲基-4-乙酰基吡咯或2,5-二吡啶基-3-羧甲基-4-甲基吡咯与顺-二氯四(二甲基亚砜)钌或二联吡啶的摩尔比为1:2~2:1。
作为一个优选的方案,所述碱性化合物为三乙胺、氢化钙、氢化钠中至少一种。这些碱性化合物主要是用于促进2,5-二吡啶基吡咯、2,5-二吡啶基-3-甲基-4-乙酰基吡咯或2,5-二吡啶基-3-羧甲基-4-甲基吡咯的脱氢反应。碱性化合物用量相对于类吡啶吡咯配体为1~8:1。
作为一个优选的方案,步骤1)中,回流反应的温度为50~115℃,时间为8~12h。
作为一个优选的方案,步骤2)中,回流反应的温度为50~115℃,时间为2~6d。
作为一个优选的方案,所述含氨气体中氨气浓度大于1%。所述含氨气体可以为纯氨气也可以为氨气与氮气或惰性气体的组合。
本发明还提供了一种类吡啶吡咯钌配合物的应用,其作为电催化氨氧化催化剂应用。
本发明提供的类吡啶吡咯钌配合物具体制备方法如下:
(1)在氮气氛围下,将2,5-二吡啶基吡咯、2,5-二吡啶基-3-甲基-4-乙酰基吡咯或2,5-二吡啶基-3-羧甲基-4-甲基吡咯配体的脱氢反应任意一种,和顺-二氯四(二甲基亚砜)钌,以及二联吡啶和碱性化合物溶解于甲苯、甲醇或四氢呋喃等溶剂中磁力搅拌加热回流8~12h,一般来说,在甲苯中回流温度在100~115℃,在四氢呋喃或甲醇中回流反应温度为50~65℃。
(2)反应完成后,在氮气氛围中分别加入甲苯、乙醚或水等溶剂进行清洗三次,随后,将所得固体溶于二氯甲烷中,并加入无水硫酸钠去除溶液中水,2小时后通过旋转蒸发仪器去除溶剂得到红色的固体,即式1、式4或式5结构钌配合物。
(3)在氮气氛围下,将式1结构类吡啶吡咯钌配合物溶于甲苯、甲醇或四氢呋喃等溶剂中,磁力搅拌加热回流反应2~6天,随后将溶液旋蒸至3mL。
(4)将饱和六氟磷酸铵水溶液滴入上述溶液中,搅拌2h后,将反应液过滤旋干得到黄色固体,即得式2结构类吡啶吡咯钌配合物。
(7)将式2结构类吡啶吡咯钌配合物溶于三氯甲烷、二氯甲烷或四氢呋喃等溶剂中,随后通入浓度为1.99%~99.99%的氨气半小时以上,静置1h,重复操作3次,放置至少两天,得到红色片状固体,即得式3结构类吡啶吡咯钌配合物。
本发明的式1~式5结构类吡啶吡咯钌配合物均具有电催化氨氧化性质,能够产生氢气、氮气和肼。如在氩气氛围中,1.0V vs.NHE过电位下电解23.5h,有375.4mmol~1458.35mmol的氢气,7.4mmol~10.55mmol的氮气,和341.2mmol~1380.04mmol的肼产生。
相对现有技术,本发明技术方案带来的有益技术效果:
本发明的类吡啶吡咯钌配合物以高活性的金属钌为中心金属离子,具有较高的给电子能力的类吡啶吡咯化合物作为配体,从而赋予了整个类吡啶吡咯钌配合物较高的氨氧化活性,将其用于氨的电催化氧化,可以实现氨的高转化率,并获得氢、氮及肼等为主的产物,具有较高选择性。
本发明的钌配合物制备方法操作和步骤简单、低成本有利于大规模生产。
附图说明
图1为配合物1[Ru(K2-N,N'-dpp)(bpy)(S-dmso)(Cl)]的单晶衍射图。
图2为配合物2[Ru(K3-N,N'N″-dpp)(bpy)(S-dmso)]·PF6的单晶衍射图。
图3为配合物3[Ru(K2-N,N'-dpp)(bpy)(S-dmso)(NH3)]·PF6的单晶衍射图。
图4为配合物4[Ru(K2-N,N'-mdpc)(bpy)(S-dmso)(Cl)]的单晶衍射图。
图5为配合物5[Ru(K3-N,N'N″-mdpe)(bpy)(Cl)]的单晶衍射图。
图6为氢气和氮气气相色谱标准曲线图。
图7 0.01mM配合物1、2和3的电催化氨氧化反应过程中气体组分图。
图8为不同反应时间,0.01mM配合物3的电催化氨氧化反应过程中气体组分图。
图9为不同反应时间,0.01mM配合物5的电催化氨氧化反应过程中气体组分图。
图10为紫外可见光谱吸收强度与肼的浓度标准曲线图。
图11为配合物1,2,3电解液与p-C9H11NO反应1h后的紫外可见吸收光谱图。
具体实施方式
为了便于理解本发明,下文将结合较佳得实施例对本发明更全面、细致地描述,但本发明得保护范围并不限于以下具体得实施例。
以下实施例中涉及的底物原料,以及溶剂等均为市售商业产品(分析纯试剂),所用试剂均经过纯化、干燥及除氧预处理,涉及的合成及处理过程使用标准无水无氧技术。其中,顺-二氯四(二甲基亚砜)钌(Nagy E M,Pettenuzzo A,Boscutti G,et al.Ruthenium(II/III)-based Compounds with Encouraging Antiproliferative Activity AgainstNon-small-cell Lung Cancer.Chemistry-A European Journal,2012,18(45):14464-14472.),2,5-二吡啶基吡咯(Imler G H,Lu Z,Kistler K A,et al.Complexes of 2,5-Bis(α-pyridyl)pyrrolate with Pd(II)and Pt(II):A Monoanionic Iso-π-ElectronLigand Analog of Terpyridine[J].Inorganic Chemistry,2012,51(19):10122-10128.)以及2,5-二吡啶基-3-甲基-4-乙酰基吡咯和2,5-二吡啶基-3-羧甲基-4-甲基吡咯(Mcsjimming A,Diachenko V,London R,et al.An Easy One-Pot Synthesis of Diverse2,5-Di(2-pyridyl)pyrroles:A Versatile Entry Point to Metal Complexes ofFunctionalised,Meridial and Tridentate 2,5-Di(2-pyridyl)pyrrolato Ligands[J].Chemistry-A European Journal,2014,20(36):11445-11456.)已有报道方法合成。
1H NMR(400MHz),31P NMR(162MHz),19F NMR(380MHz),以CDCl3为溶剂,以TMS为内标。
多重性定义如下:s(单峰);d(二重峰);t(三重峰);q(四重峰)和m(多重峰)。吸收强度定义如下:s(强吸收);m(中等程度吸收);w(弱吸收)。
除非另有定于,下文中所使用的所有专业术语与本领域技术人员通常理解的含义相同。本文所使用的专业术语只是问了描述具体实施例的目的,并不是皆在本发明的保护范围。
实施例1
1、配合物1[Ru(K2-N,N'-dpp)(bpy)(S-dmso)(Cl)]的制备目标产物
(1)在氮气氛围下,顺-二氯四(二甲基亚砜)钌(1.088g,2.248mmol),2,5-二吡啶基吡咯(0.566g,2.248mmol),二联吡啶(0.351g,2.247mmol)和三乙胺(2.4mL)溶解于甲苯溶剂(50mL)中磁力搅拌加热至105℃反应10h。
(2)反应完成后在氮气氛围中分别加入甲苯,乙醚和水清洗三次。随后,将所得固体溶于二氯甲烷中,并加入无水硫酸钠去除溶液中水,2h后通过旋转蒸发仪器去除溶剂,得到红色的固体。
(3)采用液相扩散的方法将所得红色固体溶于二氯甲烷中,依此加入乙醚和正己烷,静置2周后,得到红色的针状晶体(配合物1)。
收率:32.33%
1H NMR(400MHz,CDCl3):δ10.171-10.186(d,1H),δ9.399-9.413(d,1H),δ8.125-8.137(d,1H),δ7.914-7.934(d,1H),δ7.644-7.731(m,3H),δ7.573-7.607(t,2H),δ7.472-7.510(m,1H),δ7.099-7.169(m,4H),δ6.963-6.995(m,1H),δ6.829-6.838(d,1H),δ6.676-6.710(m,1H),δ6.299-6.309(d,1H),δ3.165(s,3H),δ2.401(s,3H)ppm.
IR(KBr,cm-1):1589(s),1522(s),1433(s),1323(s),1279(w),1152(w),1074(s),1014(s),961(w),919(w),789(m),766(s),724(m),686(m),435(m).
2、配合物2[Ru(K3-N,N'N″-dpp)(bpy)(S-dmso)]·PF6的制备
目标产物
(4)在氮气氛围下,将配合物1溶于甲醇中磁力搅拌加热60℃反应4天,随后将溶液旋蒸至3mL。
(5)将饱和六氟磷酸铵水溶液滴入上述溶液中,搅拌2h后,将反应液过滤旋干,得到黄色固体。
(6)采用液相扩散的方法将所得红色固体溶于二氯甲烷中,依此加入乙醚和正己烷,静置2周后,得到红色的针状晶体(配合物2)。
收率:93.36%。
1H NMR(400MHz,CDCl3):δ10.315-10.301(d,1H),δ8.583-8.563(d,1H),δ8.442-8.422(d,1H),δ8.177-8.138(t,1H),δ7.924-7.884(t,1H),δ7.763-7.730(t,1H),δ7.550-7.511(m,2H),δ7.418-7.399(d,2H),δ7.328-7.315(d,2H),δ7.231-7.197(t,1H),δ6.909(s,2H),δ6.823-6.809(d,1H),δ6.748-6.715(m,2H),δ2.582(s,6H)ppm.
31P NMR(162MHz,CDCl3):δ-135.60,δ-140.01,δ-144.40,δ-148.80,δ-153.20ppm.
19F NMR(380MHz,CDCl3):δ-72.36,δ-74.25ppm.
IR(KBr,cm-1):1598(s),1486(s),1396(m),1298(s),1263(w),1156(w),1087(m),1042(w),1008(m),840(s),760(s),557(s),431(m).
3、配合物3[Ru(K2-N,N'-dpp)(bpy)(S-dmso)(NH3)]·PF6的制备
目标产物
(1)将配合物2(35mg,0.050mmol)溶于三氯甲烷中,随后通入1.99%的氨气(载气为氮气)半小时,静置1h,重复3次,放置2周,最后在室温下将溶液浓缩,依次加入乙醚和正己烷,通过液相扩散法得到红色片状晶体(配合物3)。
收率:98.01%。
1H NMR(400MHz,CDCl3):δ9.871-9.858(d,1H),δ8.412-8.401(d,1H),δ8.313-8.293(d,1H),δ8.251-8.231(d,1H),δ7.714-7.675(t,1H),δ7.646-7.612(t,1H),δ7.517-7.503(d,1H),δ7.463-7.402(m,2H),δ7.328-7.315(d,2H),δ7.189-7.175(d,1H),δ7.095-7.175(d,1H),δ7.095-7.064(m,1H),δ7.029-7.019(d,1H),δ6.981-6.952(t,1H),δ6.617-6.586(t,1H),δ3.160(s,3H),δ3.110(s,3H),δ2.534(s,3H)ppm.
31P NMR(162MHz,CDCl3):δ-135.92,δ-140.28,δ-144.64,δ-149.00,δ-153.36ppm.
19F NMR(380MHz,CDCl3):δ-72.02,δ-73.89ppm.
IR(KBr,cm-1):3371(w),1604(m),1529(m),1454(w),1421(m),1325(m),1161(w),1080(m),1018(m),843(s),764(m),685(w),557(m),430(m).
表5配合物3的晶体数据
aGooF=[Σw(|Fo|-|Fc|)2/(Nobs-Nparam)]1/2.
bR1=Σ||Fo|-|Fc||/Σ|Fo|.cwR2[(Σw|Fo|-|Fc|)2/Σw2|Fo|2]1/2.
表6配合物3的部分键长键角数据.
4、配合物4[Ru(K2-N,N'-mdpc)(bpy)(S-dmso)(Cl)]制备目标产物
(1)在氮气氛围下,顺-二氯四(二甲基亚砜)钌(1.088g,2.248mmol),2,5-二吡啶基-3-羧甲基-4-甲基吡咯配体(0.659g,2.248mmol),二联吡啶(0.351g,2.247mmol)和三乙胺(2.4mL)溶解于甲苯(50mL)中磁力搅拌加热至105℃反应9h。
(2)反应完成后在氮气氛围中分别加入甲苯,乙醚和水清洗三次,随后,将所得固体溶于二氯甲烷中,并加入无水硫酸钠去除溶液中水,2h后通过旋转蒸发仪器去除溶剂,得到红色的固体。
(3)将红色固体溶于二氯甲烷中,以二氯甲烷、乙酸乙酯(v/v=2:1)为洗脱剂,使用层析硅胶柱进行柱色谱分离,收集第四个产物,得到红色固体产物。
(4)采用液相扩散的方法将所得红色固体溶于二氯甲烷中,依此加入乙醚和正己烷,静置2周后,得到红色的针状晶体(配合物[Ru(K2-N,N'-mdpc)(bpy)(S-dmso)(Cl)])。
收率:24.61%。
1H NMR(400MHz,CDCl3):δ9.677-9.689(d,1H),δ9.552-9.565(d,1H),δ8.045-8.091(t,2H),δ7.847-7.868(d,2H),δ7.738-7.796(m,2H),δ7.485-7.528(m,1H),δ7.430-7.442(d,1H),δ7.132-7.178(m,2H),δ7.026-7.062(m,1H),δ6.892-6.928(m,1H),δ6.779-6.813(m,1H),δ6.724(s,1H),δ3.290(s,3H),δ3.019(s,3H)ppm,δ2.744(s,3H)ppm,δ2.460(s,3H)ppm.
IR(KBr,cm-1):3603(m),2916(s),2497(m),1682(s),1589(m),1521(w),1444(s),1414(w),1323(w),1261(w),1198(w),1153(w),1078(s),1012(w),766(s),729(w),679(w),430(m).
5、配合物5[Ru(K3-N,N'N″-mdpe)(bpy)(Cl)]的制备目标产物
(1)在氮气氛围下,cis-[Ru(dmso)4(Cl)2](1.088g,2.248mmol),2,5-二吡啶基-3-甲基-4-乙酰基吡咯(0.623g,2.248mmol),二联吡啶(0.351g,2.247mmol)和三乙胺(2.4mL)溶解于甲苯(50mL)中磁力搅拌加热至100℃反应12h。
(2)反应完成后在氮气氛围中分别加入甲苯,乙醚和水清洗三次,随后,将所得固体溶于二氯甲烷中,并加入无水硫酸钠去除溶液中水,2h后通过旋转蒸发仪器去除溶剂,得到红色的固体。
(3)采用液相扩散的方法将所得红色固体溶于二氯甲烷中,依此加入乙醚和正己烷,静置2周后,得到红色的针状晶体(配合物5)。
收率:29.41%。
1H NMR(400MHz,CDCl3):δ10.443-10.457(d,1H),δ8.906-8.927(d,1H),δ8.159-8.179(d,1H),δ7.913-7.932(d,1H),δ7.787-7.826(t,1H),δ7.709-7.722(d,1H),δ7.612-7.645(t,1H),δ7.454-7.505(t,1H),δ7.249-7.351(m,2H),δ7.087-7.110(t,2H),δ6.847-6.886(m,2H),δ6.406-6.475(m,2H),δ2.794(s,3H),δ2.603(s,3H).
IR(KBr,cm-1):3095(w),3059(m),1631(m),1589(s),1460(s),1417(m),1354(w),1340(w),1242(w),1136(s),1020(w),982(w),945(w),754(m),619(w).
6、气相色谱实验:
(1)气相色谱测定反应过程中气体的组成,电位为1.0V(vs.NHE)电解质为包含0.01mM配合物1,2,3或5,0.1M[NBu4][PF6],和1.99M NH3的超干乙腈溶液。
(2)在电解的不同时间阶段,使用气密针取100μL上层气体注入气相色谱中,得到电解池中气体组成和含量。直到23.5h后,电解池中各气体含量改变变得缓慢,即可停止实验。
测试结果为:电解23.5h后,配合物1有375.4μmol(938.4当量)的氢气和7.4μmol(18.5当量)的氮气产生,配合物2有459.5μmol(1148.7当量)的氢气和6.32μmol(15.8当量)的氮气产生,配合物3有1458.35μmol(3645.9当量)的氢气和10.55μmol(26.4当量)的氮气产生。电解49.5h后,配合物5有86.08μmol(215.2当量)的氢气和5.85μmol(14.6当量)的氮气产生。通过气相色谱实验发现,配合物3和5电催化氨氧化过程中,氢气和系统内氮气的比例分别稳定在110:1和10:1这远远高于氨分子中氢元素与氮元素的比例(3:1),于是我们认为在电解的过程中有NH2NH2的物质产生。
7、紫外可见光谱实验:
(1)在10mL的比色皿中,加入0.4mL电解液,0.5mL HCl(0.6mol/L)溶液和0.5mL p-C9H11NO的乙醇溶液,加水稀释至10mL反应1h。
(2)取0.5mL反应液于10mL比色皿中稀释至10ml,通过紫外可见光谱仪收集455nm处的吸收强度,并带入通过标准方法制的NH2NH2浓度和吸光度标准曲(Watt G W,Chrisp JD,Spectrophotometric Method for Determination of Hydrazine.AnalyticalChemistry,1952,24(12):2006-2008.),得到电解液中NH2NH2的含量。
测试结果为:电解23.5h后,配合物1,2和3分别产生了341.2μmol(853.0当量),423.0μmol(1057.6当量)和1380.04μmol(3450.1当量)的NH2NH2。这与氢气的含量相一致,说明NH2NH2为主要产物。
以上显示和描述了本发明制备配合物1,2,3,4,5的主要方法和电催化氨氧化特性。
本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理和方法过程,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (6)
1.一种类吡啶吡咯钌配合物,其特征在于:具有式1~式5结构中任意一种:
2.权利要求1所述的一种类吡啶吡咯钌配合物的合成方法,其特征在于:包括以下步骤:
1)2,5-二吡啶基吡咯、2,5-二吡啶基-3-甲基-4-乙酰基吡咯或2,5-二吡啶基-3-羧甲基-4-甲基吡咯与顺-二氯四(二甲基亚砜)钌和二联吡啶以及碱性化合物溶于甲苯中,加热回流反应,回流反应的温度为100~115℃,时间为8~12h,即得式1、式4或式5结构类吡啶吡咯钌配合物;
2)将式1结构类吡啶吡咯钌配合物溶于甲苯中,先加热回流反应,回流反应的温度为100~115℃,时间为2~6d,再加入饱和六氟磷酸铵溶液进行离子交换反应,得到式2结构类吡啶吡咯钌配合物;
3)将式2结构类吡啶吡咯钌配合物溶于甲苯中,再通入含氨气体反应,即得式3结构类吡啶吡咯钌配合物。
3.根据权利要求2所述的一种类吡啶吡咯钌配合物的合成方法,其特征在于:2,5-二吡啶基吡咯、2,5-二吡啶基-3-甲基-4-乙酰基吡咯或2,5-二吡啶基-3-羧甲基-4-甲基吡咯与顺-二氯四(二甲基亚砜)钌或二联吡啶的摩尔比为1:2~2:1。
4.根据权利要求2所述的一种类吡啶吡咯钌配合物的合成方法,其特征在于:所述碱性化合物为三乙胺、氢化钙、氢化钠中至少一种。
5.根据权利要求2所述的一种类吡啶吡咯钌配合物的合成方法,其特征在于:所述含氨气体中氨气浓度大于1%。
6.权利要求1所述的一种类吡啶吡咯钌配合物的应用,其特征在于:作为电催化氨氧化催化剂。
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EP22909854.6A EP4261216A1 (en) | 2021-12-22 | 2022-12-15 | Pyridine pyrrole ruthenium complex, preparation method therefor and application thereof as catalyst for preparing hydrazine by electrocatalytic ammonia oxidation |
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