WO2023116540A1 - 一种吡啶吡咯钌配合物及其制备方法和作为电催化氨氧化制备肼的催化剂的应用 - Google Patents

一种吡啶吡咯钌配合物及其制备方法和作为电催化氨氧化制备肼的催化剂的应用 Download PDF

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WO2023116540A1
WO2023116540A1 PCT/CN2022/139184 CN2022139184W WO2023116540A1 WO 2023116540 A1 WO2023116540 A1 WO 2023116540A1 CN 2022139184 W CN2022139184 W CN 2022139184W WO 2023116540 A1 WO2023116540 A1 WO 2023116540A1
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ruthenium complex
pyridine
formula
pyridine pyrrole
reaction
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易小艺
陈果
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Central South University
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Priority to KR1020237024287A priority patent/KR20230119704A/ko
Priority to EP22909854.6A priority patent/EP4261216A4/en
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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • 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
    • 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
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/085—Organic compound
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/09—Nitrogen containing compounds
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • 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
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to a catalytic material, in particular to a pyridine pyrrole ruthenium complex catalytic material, and also relates to its synthesis method and its application as a catalyst for preparing hydrazine by electrocatalytic ammoxidation, belonging to the technical field of catalysis.
  • Hydrogen (H 2 ) is recognized as one of the most ideal substitutes for fossil fuels.
  • the unfavorable factors such as extremely low volumetric energy density, extremely flammable and explosive, high storage and transportation costs, and poor safety limit the large-scale direct use of hydrogen energy. Therefore, the development of hydrogen storage technology and hydrogen storage materials is imperative.
  • liquid small molecules have attracted much attention as hydrogen energy carriers.
  • Ammonia molecule (NH 3 ) has a hydrogen content as high as 17.6wt%, and has obvious advantages as a hydrogen energy carrier.
  • NH 3 Ammonia molecule
  • its development and utilization have been progressing slowly, mainly due to the half-reaction of ammonia oxidation.
  • Small-molecule metal complexes as homogeneous catalysts provide a solution for the catalytic oxidation of ammonia molecules under mild conditions.
  • N 2 H 4 also known as hydrazine
  • hydrazine a chemical reagent with strong reducibility and high energy
  • the first industrial production of N 2 H 4 was realized in 1907, after more than 100 years of development, the current industrial production of N 2 H 4 still relies on the traditional or improved Raschig method, that is, the use of strong oxidants to chemically oxidize NH 3 to prepare N 2 H 4 .
  • the traditional Raschig method requires the use of a large amount of chlorine-containing strong oxidants, causing environmental pollution problems, and the improved Raschig method also produces a large amount of organic by-products.
  • anhydrous N 2 H 4 The cost of preparing anhydrous N 2 H 4 is high.
  • the added value of anhydrous N 2 H 4 is much higher than that of hydrazine hydrate (N 2 H 4 ⁇ H 2 O), anhydrous N 2 H 4 is 450,000 yuan/ton, 80% N 2 H 4 ⁇ H 2 O is 25,000 yuan/ton Ton.
  • the Raschig method is carried out in aqueous solution, usually only hydrazine hydrate (N 2 H 4 ⁇ H 2 O) with the highest concentration of 80% can be obtained, and a high-cost dehydration process is required to obtain anhydrous N 2 H 4 .
  • thermodynamically unfavorable scientific challenge of NH 3 dehydrogenation into N 2 H 4 cannot be overcome for a long time, and the existing N 2 H 4 preparation process cannot solve the series of problems such as cumbersome operation, low yield and high energy consumption, making N 2H4 prices are high. Therefore, it is not only extremely scientifically challenging to develop a new method for efficient anhydrous N 2 H 4 preparation, but also has important application value.
  • electrocatalytic NH 3 oxidation can realize one-step co-production of two high value-added products: anhydrous N 2 H 4 and H 2 .
  • a disruptive and innovative technical route for the preparation of anhydrous N 2 H 4 Therefore, the development of catalysts for electrocatalytic ammoxidation to hydrazine has important theoretical significance and application value.
  • the first object of the present invention is to provide a pyridine pyrrole metal ruthenium complex with high catalytic activity for electrocatalytic ammoxidation.
  • the second object of the present invention is to provide a method for preparing pyridine pyrrole metal ruthenium complexes with simple operation and steps and low cost.
  • the third object of the present invention is to provide a kind of application of pyridine pyrrole ruthenium complex as electrocatalytic ammoxidation catalyst. Sexual conversion into H 2 , N 2 and N 2 H 4 .
  • the present invention provides a pyridine pyrrole ruthenium complex, which has any one of the structures of formula 1 to formula 5:
  • the pyridinepyrrole ruthenium complex of the present invention uses metal ruthenium as the central metal ion, and the pyridinepyrrole compound is used as a ligand.
  • Metal ruthenium belongs to a high-period transition metal and has multiple oxidation states (the valence range is -2 to +8 ), showing high reactivity, and the pyridine pyrrole ligand has the ability to donate/withdraw electrons, which can effectively reduce the oxidation potential of ammonia.
  • the internal hydrogen bond formed by the pyridine group of the pyridine pyrrole ligand and the ammonia molecule can accelerate ammonia The process of deprotonation in the oxidation, thus endowing the whole pyridine pyrrole ruthenium complex with high catalytic activity and high selectivity for ammoxidation.
  • the present invention also provides a synthetic method of pyridine pyrrole ruthenium complex, which comprises the following steps:
  • 2,5-dipyridylpyrrole, 2,5-dipyridyl-3-methyl-4-acetylpyrrole or 2,5-dipyridyl-3-carboxymethyl-4- The molar ratio of methylpyrrole to cis-dichlorotetrakis(dimethylsulfoxide)ruthenium is 1:2 ⁇ 2:1.
  • the molar ratio of cis-dichlorotetrakis(dimethylsulfoxide)ruthenium to bipyridine is 1:3 ⁇ 3:1.
  • the basic compound is at least one of calcium hydride, sodium hydride and triethylamine. These basic compounds are mainly used to promote 2,5-dipyridylpyrrole, 2,5-dipyridyl-3-methyl-4-acetylpyrrole - Deprotonation reaction of 4-methylpyrrole.
  • the dosage of the basic compound relative to the pyridine-like pyrrole ligand is 1-8:1.
  • the basic compounds that can promote the deprotonation reaction can be used, for example: sodium, sodium bicarbonate, sodium carbonate, sodium methylate, sodium hydroxide,
  • the reaction temperature is 50-115° C.
  • the reaction time is 8-12 hours.
  • the organic solvent is dichloromethane, chloroform, acetonitrile, methanol, tetrahydrofuran, benzene, toluene.
  • the temperature of the reflux reaction is 50-115° C., and the time is 2-6 days.
  • the ammonia concentration in the ammonia-containing gas is greater than 1%.
  • the ammonia-containing gas may be pure ammonia or a combination of ammonia and nitrogen or an inert gas.
  • the present invention also provides an application of a pyridine pyrrole ruthenium complex as a catalyst for preparing N2H4 by electrocatalytic ammoxidation while coproducing H2 .
  • the pyridine pyrrole ruthenium complexes with the structures of formula 1 to formula 5 of the present invention all have the catalytic property of electrocatalytic ammoxidation to generate H 2 , N 2 and N 2 H 4 .
  • electrolysis at a potential not lower than 0.5Vvs.Cp 2 Fe +/0 for 0 to 72 hours, with 0 to 2500 ⁇ mol of H 2 , 0 to 25 ⁇ mol of N 2 , and 0 to 2500 ⁇ mol of N 2 H4 produced.
  • the conversion rate of NH 3 into N 2 H 4 can be as high as 45%, the solubility of N 2 H 4 in the electrolyte reaches 0.032mol/L, and the high Faradaic efficiency FE is 50-92%.
  • the pyridine pyrrole ruthenium complex of the present invention uses highly active metal ruthenium as the central metal ion, and the pyridine pyrrole compound with the ability to pull/donate electrons is used as a ligand, thereby endowing the entire pyridine pyrrole ruthenium complex with higher ammoxidation catalysis active.
  • the preparation method of the pyridinepyrrole ruthenium complex of the present invention has simple operation and steps, low cost and is favorable for large-scale production.
  • the pyridinepyrrole ruthenium complex of the present invention can realize high selectivity (n N2H4 /n N2max 200), high catalytic efficiency (TOF N2H4max 400h -1 ), high Faradaic efficiency FE max 92%) electrocatalytic NH3 oxidation in one step Prepare anhydrous N 2 H 4 and co-produce H 2 at the same time.
  • the pyridinepyrrole ruthenium complex of the present invention can be prepared by one-step N 2 H 4 in a pure organic solvent, which is convenient for separation and purification.
  • N 2 H 4 is still the traditional Raschig method and non-catalytic oxidation route, which has the problems of cumbersome process route, low yield, high energy consumption and serious pollution.
  • the pyridinepyrrole ruthenium complex of the present invention only takes the electrocatalytic oxidation at normal temperature and pressure as the reaction scene, and synthesizes two valuable products in one step, and the separation steps are extremely simple, which can be used for the next step of industrialized anhydrous N 2 H 4 Production provides disruptive innovative technologies.
  • Figure 1 is the single crystal diffraction pattern of complex 1 [Ru(K 2 -N,N'-dpp)(bpy)(S-dmso)(Cl)];
  • Figure 2 is the single crystal diffraction pattern of complex 2 [Ru(K 3 -N,N'N′′-dpp)(bpy)(S-dmso)] ⁇ PF 6 ;
  • Figure 3 is the single crystal diffraction pattern of complex 3 [Ru(K 2 -N,N'-dpp)(bpy)(S-dmso)(NH 3 )] ⁇ PF 6 ;
  • Figure 4 is the single crystal diffraction pattern of complex 4 [Ru(K 2 -N,N'-mdpc)(bpy)(S-dmso)(Cl)];
  • Figure 5 is a single crystal diffraction pattern of complex 5 [Ru(K 3 -N,N'N"-mdpe)(bpy)(Cl)];
  • Fig. 6 is hydrogen and nitrogen gas chromatography standard curve figure
  • Figure 70 Gas composition diagram during the electrocatalytic ammoxidation reaction of 01mM complexes 1, 2 and 3;
  • Fig. 8 is different reaction time, the gas component diagram in the electrocatalytic ammoxidation reaction process of 0.01mM complex 3;
  • Fig. 9 is a diagram of gas components in the electrocatalytic ammoxidation reaction process of 0.01mM complex 5 at different reaction times;
  • Fig. 10 is the concentration standard curve figure of ultraviolet-visible spectrum absorption intensity and hydrazine
  • Fig. 11 is the ultraviolet-visible absorption spectrum of complexes 1, 2, and 3 electrolytes reacted with pC 9 H 11 NO for 1 hour.
  • the substrate raw materials and solvents involved in the following examples are all commercially available products (analytical pure reagents).
  • the reagents used are all purified, dried and deoxidized. processing technology.
  • 1 H NMR, 31 PNMR, and 19 F NMR use CDCl 3 as the solvent and TMS as the internal standard.
  • Multiplicity is defined as follows: s (singlet); d (doublet); t (triplet); q (quartet) and m (multiplet).
  • Absorption intensity is defined as follows: s (strong absorption); m (moderate absorption); w (weak absorption).
  • red solid was dissolved in dichloromethane by the method of liquid phase diffusion, ether and n-hexane were added accordingly, and after standing for 2 weeks, red needle-like crystal complex 1 was obtained.
  • red solid was dissolved in dichloromethane by the method of liquid phase diffusion, ether and n-hexane were added accordingly, and after standing for 2 weeks, red needle-like crystal complex 2 was obtained.
  • Dissolve complex 2 (35mg, 0.050mmol) in chloroform, then pass through 2% ammonia gas (nitrogen as the carrier gas) for half an hour, let stand for 1h, repeat 3 times, let stand for 2 weeks, and finally The solution was concentrated at room temperature, ether and n-hexane were added sequentially, and the complex 3 was obtained as a red flaky crystal by liquid phase diffusion method.
  • red solid was dissolved in dichloromethane by liquid phase diffusion, ether and n-hexane were added in sequence, and after standing for 2 weeks, red needle-like crystal complex 4 was obtained.
  • red solid was dissolved in dichloromethane by the method of liquid phase diffusion, ether and n-hexane were added accordingly, and after standing for 2 weeks, red needle-like crystal complex 5 was obtained.
  • composition of the gas during the reaction is determined by gas chromatography, the test conditions: the potential is not lower than 0.5V vs Cp 2 Fe +/0 , the electrolyte contains 0-0.1mM complex 1, 2, 3, 4 or 5, 0.1 M[NBu 4 ][PF 6 ], and an organic solution of 0-2.5M NH 3 .
  • test results are: after electrolysis for 24 hours, complexes 1, 2 and 3 produced 341.2 ⁇ mol, 423.0 ⁇ mol and 1380.04 ⁇ mol of NH 2 NH 2 , respectively.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Pyridine Compounds (AREA)
PCT/CN2022/139184 2021-12-22 2022-12-15 一种吡啶吡咯钌配合物及其制备方法和作为电催化氨氧化制备肼的催化剂的应用 Ceased WO2023116540A1 (zh)

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US18/272,369 US20240101586A1 (en) 2021-12-22 2022-12-15 Pyridine pyrrole ruthenium coordination complex, preparation method therefor and use thereof as catalyst for electrocatalyzing ammonia oxidation to prepare hydrazine
JP2023524432A JP7629655B2 (ja) 2021-12-22 2022-12-15 ピリジン－ピロール－ルテニウム錯体とその生成方法、及びアンモニア酸化に対し電極触媒作用を発揮してヒドラジンを生成する触媒としての応用
KR1020237024287A KR20230119704A (ko) 2021-12-22 2022-12-15 피리딘피롤루테늄 배위결합복합체, 이의 제조방법 및암모니아의 전기 촉매 산화에 의한 하이드라진 제조를 위한 촉매제로서의 응용
EP22909854.6A EP4261216A4 (en) 2021-12-22 2022-12-15 PYRIDINE PYRROLE RUTHENIUM COMPLEX, PROCESS FOR ITS PREPARATION AND ITS USE AS A CATALYST FOR THE PREPARATION OF HYDRAZINE BY ELECTROCATALYTIC OXIDATION OF AMMONIA

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CN114853798B (zh) * 2022-06-07 2024-07-02 海南贝欧亿科技有限公司 一种吡咯环三齿金属配合物及其应用
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* Cited by examiner, † Cited by third party
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CN114478648A (zh) * 2021-12-22 2022-05-13 中南大学 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
CN114478648B (zh) * 2021-12-22 2024-01-30 中南大学 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

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EP4261216A1 (en) 2023-10-18
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CN114478648A (zh) 2022-05-13
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