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WO2017010771A1 - Method for regenerating metal-organic framework - Google Patents

Method for regenerating metal-organic framework Download PDF

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Publication number
WO2017010771A1
WO2017010771A1 PCT/KR2016/007510 KR2016007510W WO2017010771A1 WO 2017010771 A1 WO2017010771 A1 WO 2017010771A1 KR 2016007510 W KR2016007510 W KR 2016007510W WO 2017010771 A1 WO2017010771 A1 WO 2017010771A1
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Prior art keywords
metal
hkust
organic framework
acid
mof
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French (fr)
Korean (ko)
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나명수
한승완
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UNIST Academy Industry Research Corp
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UNIST Academy Industry Research Corp
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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • 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
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
    • B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof

Definitions

  • the present invention relates to a method for regenerating a metal-organic framework (M0F).
  • the present invention relates to a method for simply and efficiently regenerating a metal-organic skeleton whose porosity is damaged by water or the like through an acid-base treatment.
  • Metal-organic frameworks have received a lot of attention as potential potential materials for gas separation, storage, and catalysts.
  • M0F-5 has a large pore volume with a large surface area.
  • practical applications are limited due to instability in atmospheric conditions.
  • HKUST Hl see Hong Kong Univers i ty of Science and Techno l ogy- 1; Chui. Et al., Science 1999, 283, 1148-50
  • HKUST-1 is one of the most studied metal-organic frameworks.
  • the hydrothermal stability of HKUST-1 is better than M0F-5, but still poor for continuous use.
  • the present invention provides a method for treating a damaged metal-organic framework (M0F) with an acid; And (2) regenerating the acid-treated metal-organic framework by amide treatment or base treatment.
  • M0F damaged metal-organic framework
  • the damaged metal-organic skeleton can be simply dissolved in strong acid and used for regeneration, the pH of the solution can be adjusted by internal base generation or external base addition, and the regeneration yield is excellent.
  • This method uses damaged metal-organic frameworks as reactions to regenerate at high yields. It is cost effective because it is environmentally friendly and can recycle expensive ligands.
  • the external base addition method is a little more environmentally friendly to the reaction can proceed without using a solvent containing the amide at room temperature, it can be applied to a large scale batch recycling reaction.
  • FIG. 1 is a schematic representation of a method of dissolving a damaged metal-organic framework in accordance with the present invention in a strong acid and regulating by regulating the pH by internal base generation or external base addition.
  • FIG. 2A shows Powder X-Ray Diffraction (PXRD) patterns of M0F-5, damaged M0F-5 and regenerated M0F-5 immediately after synthesis
  • FIG. 2B shows M0F-5, damaged M0F-5 and regenerated postsynthesis. The nitrogen adsorption isotherm of M0F-5 is shown.
  • PXRD Powder X-Ray Diffraction
  • FIG. 3 shows SEM of (a) initial HKUST-KBasolite C300), (b) damaged HKUST-1, (c) HKUST-1 regenerated from nitric acid containing solution, and (d) HKUST-1 regenerated from hydrochloric acid containing solution. It represents an image.
  • Figure 5 shows SEM images of (a) MOF-5 immediately after synthesis, (b) damaged M0F-5, and (c) regenerated M0F-5.
  • FIG. 15 is an SEM image of HKUST-1 regenerated 1 minute after addition of NaOH solution.
  • FIG. 16 is an IR spectrum of HKUST-1 regenerated after 1 minute from addition of NaOH solution.
  • FIG. 17 is the PXRD pattern of initial state HKUST-1 and HKUST-1 regenerated 1 minute after addition of NaOH solution.
  • 19 is an SEM image of HKUST-1 regenerated from a mixture of four different damaged HKUST-1 samples.
  • HKUST-l is an IR spectrum of HKUST-l regenerated from a mixture of initial state HKUST-l and four different damaged HKUST-l samples.
  • FIG. 21 is a PXRD pattern of HKUST-l regenerated from a mixture of initial HKUST-l and four different damaged HKUST-l samples.
  • FIG. 22 shows initial HKUST-l and four different damaged HKUST-l samples. Nitrogen adsorption isotherm of HKUST-1 regenerated from the mixture.
  • the method for regenerating a metal-organic framework comprises the steps of: (1) treating a damaged metal-organic framework (M0F) with an acid; And (2) regenerating the acid treated metal-organic framework by amide treatment or base treatment.
  • M0F damaged metal-organic framework
  • the above steps may be performed sequentially or simultaneously.
  • the damaged metal-organic framework can be regenerated by treatment with an acid and simultaneously with amide treatment or base treatment.
  • Metal-Organic Framework The metal-organic framework (M0F) targeted in the present invention is not particularly limited, and may be, for example, a metal-organic framework having porosity.
  • the metal-organic framework is M0F-5 (IRM0F-1), HKUST-1, IRMOF-2, IRMOF-3, IRMOF-4, IRMOF-5, IRMOF-6, IRMOF-7, IRMOF- 8, IRMOF-9, IRMOF-10, IRMOF-ll, IRMOF-12, IRMOF-13, IRMOF-14, IRMOF-15, IRMOF-16, M0F-74 (Mg), M0F-74 (Fe), M0F- 74 (Co), M0F-74 (Ni), M0F-74 (Zn), MOF-14, MOF-177, MOF—508, UMCM-1, DUT-9, UiO-BPY, UiO-67, ZrMOF-BIPY And UiO-68, MOF-802, MOF-804, MOF-805, MOF-806, and MOF-808.
  • the specific structure (composition) of the metal-organic framework is M0
  • IRMOF-5 Zn40 (BDC-0C5Hn) 3
  • IRM0F-7 Zn 4 0 (BDOC 4 H 4 ) 3
  • MOF-177 Zn 4 0 (BTB) 2
  • MOF-508 Zn 2 (BDC) 2 (BPY)
  • DC BDC- (OH) 2 2, 5-d i hydroxy- 1, 4-benzened i carboxy 1 at e
  • the damaged metal-organic framework may be at least one of the various metal-organic frameworks exemplified above.
  • the damaged metal-organic framework refers to a metal-organic framework that has been degraded or degraded, or deteriorated or deteriorated.
  • the damaged metal-organic framework is water, steam, hydrochloric acid, nitric acid, sulfuric acid phosphoric acid, acetic acid, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, acetone, carbon tetrachloride, chloroform, dichloromethane, dimethylacetamide, diethylformamide, dimethyl sulfoxide And metal-organic frameworks damaged by sides, benzene, toluene, methanol, ethane, propanol, isopropyl alcohol and the like.
  • the damaged metal-organic framework may comprise a metal-organic framework damaged by water or steam.
  • the damaged metal-organic framework has a porosity and / or BET specific surface area of 99% or less, 90% or less, 80% or less, compared to the metal-organic framework in its initial state immediately after synthesis from the raw material. It can mean a metal-organic framework that is 70% or less.
  • Acid Treatment This step is a step of treating the damaged metal-organic framework (M0F) with an acid.
  • the type of acid used in this step is not particularly limited, but is preferably a strong acid.
  • nitric acid (HN0 3 ), hydrochloric acid (HC1), acetic acid, formic acid, hydrofluoric acid and the like can be used as the acid.
  • the metal-organic framework is generally weak to acids because it is composed of ligands containing carboxyl groups, and the metal-organic frameworks damaged by water are also composed of ligands containing metal ions and carboxyl groups and can be easily dissolved by addition of strong acids. . Damaged metal-organic frameworks contain the same stoichiometric ratios of metal ions and ligands as the metal-organic frameworks before they are damaged. Conditions similar to those required for synthesis.
  • the acid treatment can be carried out in a solvent, for example by adding a solvent and / or an acid to the damaged metal-organic framework.
  • the acid treatment is performed by treating the damaged metal-organic framework with d- 3 alcohol, water, dimethylformamide, acetone, carbon tetrachloride, chloroform, dichloromethane, dimethylacetamide, diethylformamide, dimethylsulfoxide, It may be carried out by stirring in benzene, toluene, or a mixed solvent thereof.
  • Base conditions reaction regeneration reaction
  • This step is a step of regenerating the acid-treated metal-organic framework by amide treatment or base treatment.
  • the regeneration step can be formed in two ways: (i) internal base production (ie in situ pathway) or (ii) external base addition (ie ex situ pathway). Regeneration reaction through internal base generation
  • the regenerating step by treating with amide may include stirring the acid treated metal-organic framework in an amide solvent under a temperature condition of 60 to 150 ° C.
  • the reaction temperature during the amide treatment may be 70 to 120 ° C if more limited.
  • the basic solvent may be added in an amount of 0.75 to 1.25 equivalents, 0.75 to 1.1 equivalents, and 0.9 to 1.1 equivalents based on 1 equivalent of the acid.
  • the basic solvent may be added in an amount of 0.75 to 1 equivalent based on 1 equivalent of the acid.
  • 1 equivalent of base to 1 equivalent of acid means an amount corresponding to the number of moles of base that can neutralize the amount of 1 mole of acid.
  • Nonstoichiometric Reaction may be a non-stoichiometric reaction in terms of the ratio of metal and ligand.
  • the regeneration reaction i.e., the amide treatment or the base treatment can be carried out in the above in s i tu or ex s i tu route after further addition of metal ions to the acid treated metal-organic framework.
  • the addition amount of the metal ions is not particularly limited, but for example, 1 to 50% ⁇ 10 to 40%, or 1 to 30% of the number of moles of metal ions contained in the acid-treated metal-organic framework solution Moles of metal ions can be added.
  • Regenerated Metal-Organic Skeletal The regenerated metal-organic framework, which has undergone more than one step, is prepared in contrast to the metal-organic framework before damage (the initial metal-organic framework just after synthesis from the raw material). Porosity and BET specific surface area of more than% can be recovered.
  • the regenerated metal-organic framework can recover porosity of at least 90%, at least 95% and even at least 98% relative to the metal-organic framework prior to damage.
  • Ethanol was purchased from B & J.
  • Powder X-ray diffraction was performed using Bruker D2 PHASER.
  • Infrared spectra were measured using a ThermoFisher Scientifc iS10 FT—IR spectrometer.
  • HKUST-1 was prepared according to the prior art (S. Xiang et al., J. Am. Chem. Soc. 2009, 131, 12415.).
  • Preparation Example 2 Preparation of Damaged Metal-Organic Skeletal
  • 0.2 mL of a 70% nitric acid solution was prepared with 50 mL of DEF, and 0.25 g of the damaged MOF-5 obtained in Preparation Example 2-1 was dissolved therein.
  • Example 2 Regeneration of HKUST-1 Through Internal Base Production
  • lOmL of 1M nitric acid solution or 1M hydrochloric acid solution, and DMF / EtOH / 3 ⁇ 40 (2: 2 : 1, v / v / v) 50mL was added stirring.
  • the reaction solution was stored for 1 day at 70 ° C. Obon.
  • the solvent was replaced several times for 2 days with DMF and acetone. Samples were dried for 1 day at 120 ° C. in vacuum.
  • the recovery yield was 0.87 g (87%) with nitric acid and 0.70 g (70%) with hydrochloric acid.
  • Example 4 HKUST-1 Regeneration from Mixtures of Different Damage Samples 8.0 g of the mixture of damaged samples obtained in Preparation Example 2-3 was prepared using a 1M HC1 solution.
  • Example 1 Analysis of Regenerated M0F-5 Through Internal Base Production
  • the damaged M0F-5 sample was dissolved in nitric acid solution and M0F-5 was regenerated to the initial state through solvent heat reaction with DEF. .
  • Example 2 Analysis of HKUST-1 Regenerated by Internal Base Production
  • the damaged HKUST-1 was dissolved in a strong acid solution and then subjected to solvent thermal reaction in a mixed solvent of DMF / EtOH / 3 ⁇ 40 to measure the micrometer size.
  • HKUST-1 crystals were obtained (see FIGS. 3 and 7 and 8).
  • Nitrogen adsorption, etc. of HKUST-1 was the same as the initial state HKUST-1 (see Fig. 9).
  • the BET specific surface area of the reproduced HKUST-1 samples (1820 or 1840 m 2 / g) was the same as the specific surface area of the initial state HKUST-1 (1840 m 2 / g).
  • recovery yield there was a slight difference depending on the type of acid. Specifically, the recovery yield of nitric acid treated HKUST-1 reached about 9OT, and hydrochloric acid. The recovery yield of treated HKUST-1 was found to be about 70%.
  • Example 3 Analysis of HKUST-1 Regenerated by External Base Addition
  • HKUST-1 was added only outside the base, without using an amide solvent. Damaged HKUST-1 was regenerated by adjusting to a pH suitable for network structure formation.
  • HKUST-1 The IR spectrum of HKUST-1 regenerated by external base addition was the same as the initial state HKUST-1 (see FIG. 10).
  • the damaged HKUST-1 was first dissolved using a strong acid solution such as HC1 solution, and an appropriate amount of NaOH solution was added to adjust the pH of the solution. .
  • HKUST-1 could be regenerated (see FIG. 11).
  • the PXRD pattern of HKUST-1 regenerated by adding 0.775 equivalents of base per equivalent of acid was the same as that of HKUST-1 in the initial state (see FIG. 4A), and the porosity of the regenerated HKUST-1 was also in the initial state.
  • the recovery rate of HKUST-1 was only 38%.
  • the base was added in the same amount, the recovery yield of regenerated HKUST-1 reached a very high value of 87%.
  • HKUST-1 was difficult to regenerate.
  • the PXRD pattern of the crystal product obtained by adding 1.25 equivalents of sodium hydroxide to 1 equivalent of acid was different from that of HKUST-1 in the initial state.
  • the BET specific surface area calculated from the nitrogen adsorption line and the like of the crystal product was only 270 m 2 / g.
  • the dimensions of HKUST-1 crystals regenerated by external base addition are much smaller than those of HKUST— regenerated by internal base generation, the BET specific surface area of these regenerated HKUST-1 are all independent of the regeneration procedure. Same as the initial HKUST-1.
  • the HKUST-1 Unlike the restoration of the M0F-5, which is affected by the type of acid, the HKUST-1
  • HKUST-1 can be regenerated from a solution in which damaged HKUST-1 is dissolved in nitric acid (see FIGS. 12-14).
  • the crystalline HKUST-1 could be recovered in about 92% yield (see FIG. 19).
  • the regenerated HKUST-1 was compared with the initial state of HKUST-1 through IR spectra, PXRD and nitrogen adsorption tests (see FIGS. 20 to 22).
  • the PXRD pattern and IR spectrum of the regenerated HKUST-1 were identical to those of the initial HKUST-1, and the porosity of the regenerated HKUST-1 was comparable to that of the initial HKUST-1.

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Abstract

The present invention relates to a method for simply and efficiently regenerating a metal-organic framework (MOF), which has porosity damaged by water or the like, through acid-base treatment, wherein the method comprises the steps of: treating a damaged metal-organic framework with an acid; and regenerating the acid-treated metal-organic framework through an amide treatment or a base treatment. According to the method, the damaged metal-organic framework can be used for regeneration by being simply dissolved in a strong acid; the pH of a solution can be adjusted by forming an internal base and adding an external base; and the regenerating yield is excellent.

Description

Γ명세서】  Γ Specifications]

【발명의 명칭】  [Name of invention]

금속 -유기 골격체의 재생방법  Regeneration method of metal-organic framework

【기술분야】 Technical Field

본 발명은 금속 -유기 골격체 (metal -organi c framework : M0F)의 재생방법에 관한 것이다.  The present invention relates to a method for regenerating a metal-organic framework (M0F).

보다 구체적으로， 본 발명은 물 등에 의해 다공성이 손상된 금속 -유기 골격체를 산 -염기 처리를 통하여 간단하고 효율적으로 재생하는 방법에 관한 것이다.  More specifically, the present invention relates to a method for simply and efficiently regenerating a metal-organic skeleton whose porosity is damaged by water or the like through an acid-base treatment.

【배경기술】 Background Art

금속 -유기 골격체 (metal-organi c framework ; M0F)는 가스 분리， 저장， 촉매 등의 잠재적인 웅용이 가능한 물질로서 많은 주목을 받고 있다. 그러나 제한된 내구성 (열적-화학적 안정성)으로 인해 실제 웅용에 있어 많은 어려움을 겪고 있다. 대표적인 금속 -유기 골격체 중 하나인 M0F-5는 거대한 표면적과 함께 커다란 기공 부피를 가지고 있다. 하지만， 실질적인 응용은 대기조건에서의 불안정성으로 인해 제한되어 있다. 또한， HKUSTᅳ l(Hong Kong Univers i ty of Sc i ence and Techno l ogy- 1； Chui . et al . , Science 1999 , 283 , 1148-50 참조)은 가장 많이 연구된 금속 -유기 골격체 중 하나로 높은 메탄 및 이산화탄소 포집 능력을 가졌다. HKUST-1의 열수 안정성은 M0F-5보다 낫지만 지속적인 사용에는 여전히 좋지 않다. HKUST-1의 흡습 조건에서 제한된 내구성은 운영비의 인상을 야기한다. 따라서， 흡습 조건에서 내구성이 개선된 금속 -유기 골격체로 대체하거나 값싸고 효율적인 HKUST-1의 합성 방법이 개발되어야 한다. 한편， 재활용 또한 금속 -유기 골격체를 싸고 효율적으로 만들 수 있는 대안점이 될 수 있다. 이와 같은 재활용은 주 반응물질에 대한 준비 비용이 들지 않고 오직 재생 과정과 연관된 합성 비용만이 소요될 수 있다. Metal-organic frameworks (M0Fs) have received a lot of attention as potential potential materials for gas separation, storage, and catalysts. However, due to the limited durability (thermal-chemical stability), there are many difficulties in practical use. One of the representative metal-organic frameworks, M0F-5, has a large pore volume with a large surface area. However, practical applications are limited due to instability in atmospheric conditions. HKUST Hl (see Hong Kong Univers i ty of Science and Techno l ogy- 1; Chui. Et al., Science 1999, 283, 1148-50) is one of the most studied metal-organic frameworks. Has high methane and carbon dioxide capture capacity. The hydrothermal stability of HKUST-1 is better than M0F-5, but still poor for continuous use. Limited durability under the hygroscopic conditions of HKUST-1 results in an increase in operating costs. Therefore, a method of synthesizing HKUST-1 or replacing a metal-organic framework having improved durability in hygroscopic conditions or inexpensive and efficient should be developed. On the other hand, recycling also makes metal-organic frameworks cheap and efficient. It may be an alternative. This recycling does not incur the cost of preparation for the main reactants and only the synthesis costs associated with the regeneration process.

최근， 증기로 손상된 HKUST-1를 손쉬운 단일 과정의 재생 기술이 보고되었다 (Majano, G. et al . , Adv. Func. Mater. 2014, 24, 3855-3865 참조). 상기 기술에 따르면， 에탄올 처리로 고정상 반웅기 (fixed bed reactor) 내에 있는 손상된 HKUST-1의 다공성을 94%까지 복구하고 있으나， 물로 다량의 손상이 발생한 경우에는 에탄올 처리만으로는 층분한 재생이 어려운 문제가 있다.  Recently, a simple single process regeneration technique for steam damaged HKUST-1 has been reported (see Majano, G. et al., Adv. Func. Mater. 2014, 24, 3855-3865). According to the above technique, ethanol treatment recovers the porosity of damaged HKUST-1 in a fixed bed reactor up to 94%. However, when a large amount of damage occurs with water, ethanol treatment alone is difficult to regenerate. have.

또한ᅳ HKUST-1을 기계화학적 방식에 의해 빠르게 재생하는 기술이 보고되었으나 (X. Sun et al. , Che . Coinmun. 2015, 51, 10835-10838 참조)， 이와 같은 방식에 의해 회복될 경우， BET 비표면적이 용매열 반웅에 의해 합성된 직후의 HKUST-1에 대비하여 대략 60%에 볼과한 한계가 있다.  In addition, a technique for rapidly regenerating HKUST-1 by a mechanochemical method has been reported (see X. Sun et al., Che. Coinmun. 2015, 51, 10835-10838), but when recovered by this method, BET There is a limit of approximately 60% relative to HKUST-1 immediately after the specific surface area is synthesized by solvent heat reaction.

【발명의 상세한 설명】 [Detailed Description of the Invention]

【기술적 과제】  [Technical problem]

본 발명의 목적은 물 둥에 의해 다공성이 손상된 금속 -유기 골격체를 간단하고 효율적인 절차 및 높은 회복 수율로 재생하는 방법을 제공하는 것이다.  It is an object of the present invention to provide a method for regenerating a metal-organic framework in which porosity is damaged by water spouts with a simple and efficient procedure and high recovery yield.

【기술적 해결방법】 Technical Solution

상기 목적에 따라， 본 발명은 (1) 손상된 금속 -유기 골격체 (metal -organic framework: M0F)를 산으로 처리하는 단계; 및 (2) 상기 산 처리된 금속 -유기 골격체를 아미드 처리하거나 염기 처리하여 재생하는 단계를 포함하는， 금속 -유기 골격체의 재생방법을 제공한다.  In accordance with the above object, the present invention provides a method for treating a damaged metal-organic framework (M0F) with an acid; And (2) regenerating the acid-treated metal-organic framework by amide treatment or base treatment.

【발명의 효과】 【Effects of the Invention】

본 발명의 재생 방법에 따르면， 손상된 금속 -유기 골격체를 단순히 강산에 녹여서 재생에 사용할 수 있고， 용액의 pH를 내부 염기 생성 또는 외부 염기 추가 방식으로 조절할 수 있으며， 재생 수율도 우수하다. 이러한 방법은 손상된 금속- 유기 골격체를 반웅물로 사용하여 높은 수득률로 재생시키기 때문에 환경친화적이고， 또한 비싼 리간드를 재생할 수 있기 때문에 가격 효율이 좋다. 특히， 외부 염기 첨가 방식은 실온에서 아미드가 들어가는 용매를 사용하지 않고 반웅을 진행할 수 있어 조금 더 환경친화적이라 할 수 있으며， 큰 스케일의 배치식 재활용 반웅에도 적용되어 사용될 수 있다. According to the regeneration method of the present invention, the damaged metal-organic skeleton can be simply dissolved in strong acid and used for regeneration, the pH of the solution can be adjusted by internal base generation or external base addition, and the regeneration yield is excellent. This method uses damaged metal-organic frameworks as reactions to regenerate at high yields. It is cost effective because it is environmentally friendly and can recycle expensive ligands. In particular, the external base addition method is a little more environmentally friendly to the reaction can proceed without using a solvent containing the amide at room temperature, it can be applied to a large scale batch recycling reaction.

【도면의 간단한 설명】 [Brief Description of Drawings]

도 1은 본 발명에 따라 손상된 금속 -유기 골격체를 강산에 용해시키고 내부 염기 생성 또는 외부 염기 첨가에 의해 pH를 조절하여 재생시키는 방법을 도식적으로 나타낸 것이다.  1 is a schematic representation of a method of dissolving a damaged metal-organic framework in accordance with the present invention in a strong acid and regulating by regulating the pH by internal base generation or external base addition.

도 2a는 합성직후의 M0F-5, 손상된 M0F-5 및 재생된 M0F-5의 PXRD(Powder X-Ray Diffraction) 패턴올 나타내고, 도 2b는 합성직후의 M0F-5, 손상된 M0F-5 및 재생된 M0F-5의 질소 흡착 등온선을 나타낸다.  2A shows Powder X-Ray Diffraction (PXRD) patterns of M0F-5, damaged M0F-5 and regenerated M0F-5 immediately after synthesis, and FIG. 2B shows M0F-5, damaged M0F-5 and regenerated postsynthesis. The nitrogen adsorption isotherm of M0F-5 is shown.

도 3은 (a) 초기상태 HKUST-KBasolite C300) , (b) 손상된 HKUST-l, (c) 질산 함유 용액으로부터 재생된 HKUST-1, 및 (d) 염산 함유 용액으로부터 재생된 HKUST-1의 SEM 이미자를 나타낸 것이다.  FIG. 3 shows SEM of (a) initial HKUST-KBasolite C300), (b) damaged HKUST-1, (c) HKUST-1 regenerated from nitric acid containing solution, and (d) HKUST-1 regenerated from hydrochloric acid containing solution. It represents an image.

도 4a는 초기상태 HKUST-1, 및 HC1 ： NaOH = 1:0.75， 1:1 및 1:1.25의 비율의 용액과 각각 반웅하여 재생된 HKUST-1의 PXRD 패턴을 나타낸다. 도 4b는 초기상태 HKUST-1, 및 HC1 ： NaOH = 1:0.75， 1:1 및 1:1.25의 비율의 용액과 각각 반웅하여 재생된 HKUST-1의 질소 흡착 등온선을 나타낸다.  FIG. 4A shows the PXRD pattern of HKUST-1 regenerated by reacting with solutions of the initial state HKUST-1 and HC1: NaOH = 1: 0.75, 1: 1 and 1: 1.25, respectively. 4B shows the nitrogen adsorption isotherm of HKUST-1 regenerated by reacting with a solution of the initial state HKUST-1, and HC1: NaOH = 1: 0.75, 1: 1 and 1: 1.25, respectively.

도 5는 (a) 합성직후의 MOF-5, (b) 손상된 M0F-5, 및 (c) 재생된 M0F-5의 SEM 이미지를 나타낸다.  Figure 5 shows SEM images of (a) MOF-5 immediately after synthesis, (b) damaged M0F-5, and (c) regenerated M0F-5.

도 6은 합성직후의 M0F-5, 손상된 M0F-5, 및 재생된 M0F-5의 IR(Infrared Spectroscopy) 스펙트럼을 나타낸다.  FIG. 6 shows Infrared Spectroscopy (IR) spectra of M0F-5, damaged M0F-5, and regenerated M0F-5 immediately after synthesis.

도 7은 초기상태 HKUST-1, 손상된 HKUST-1, 질산 함유 용액으로부터 재생된 HKUST-1, 및 염산 함유 용액으로부터 재생된 HKUST-1의 PXRD 패턴이다. 도 8은 초기상태 HKUST-1, 손상된 HKUST-l, 질산 함유 용액으로부터 재생된 HKUST-1, 및 염산 함유 용액으로부터 재생된 HKUST-1의 IR 스펙트럼이다. 도 9는 초기상태 HKUST-1, 손상된 HKUST-1, 질산 함유 용액으로부터 재생된 HKUST-l, 및 염산 함유 용액으로부터 재생된 HKUST-1의 질소 흡착 등온선이다. 7 is a PXRD pattern of initial state HKUST-1, damaged HKUST-1, HKUST-1 regenerated from nitric acid containing solution, and HKUST-1 regenerated from hydrochloric acid containing solution. 8 is an IR spectrum of the initial state HKUST-1, damaged HKUST-1, HKUST-1 regenerated from nitric acid containing solution, and HKUST-1 regenerated from hydrochloric acid containing solution. 9 shows initial HKUST-1, damaged HKUST-1, from nitric acid containing solution. HKUST-1 regenerated, and nitrogen adsorption isotherm of HKUST-1 regenerated from hydrochloric acid containing solution.

도 10은 초기상태 HKUST-l, 및 HC1 ： NaOH = 1:0.75， 1:1 및 1:1.25의 비율의 용액과 각각 반웅하여 재생된 HKUST-l의 IR스펙트럼이다.  Fig. 10 shows IR spectra of HKUST-l regenerated by reacting with solutions of the initial state HKUST-l and HC1: NaOH = 1: 0.75, 1: 1 and 1: 1.25, respectively.

도 11은 HC1 ： NaOH = 1:0.75(a), l:l(b) 및 1:1.25(c)의 비율의 용액과 각각 반웅하여 재생된 HKUST-l의 SEM 이미지이다.  FIG. 11 is an SEM image of HKUST-1 regenerated by reacting with a solution of HC1: NaOH = 1: 0.75 (a), l: l (b) and 1: 1.25 (c), respectively.

도 12는 질산 (HN03) ： NaOH = 1:0.75， 1:0.9, 1:1， 1:1.1 및 1:1.25의 비율의 용액과 각각 반웅하여 재생된 HKUST-l의 IR스펙트럼이다. 12 is an IR spectrum of HKUST-1 regenerated by reacting with a solution of nitric acid (HNO 3 ): NaOH = 1: 0.75, 1: 0.9, 1: 1, 1: 1.1 and 1: 1.25, respectively.

도 13은 초기상태 HKUST-l, 및 질산 ： NaOH = 1:0.75， 1:0.9, 1:1ᅳ 1:1.1， 1:1.25 및 1:1.5의 비율의 용액과 각각 반웅하여 재생된 HKUST-l의 PXRD 패턴이다. 도 14는 초기상태 HKUST-l, 및 질산 ： NaOH = 1:0.75， 1:0.9， 1:1， 1:1.1 및 1:1.25의 비율의 용액과 각각 반웅하여 재생된 HKUSTᅳ 1의 질소 홉착 등온선이다.  13 shows HKUST-l regenerated by reaction with a solution of the initial state HKUST-l, and nitric acid: NaOH = 1: 0.75, 1: 0.9, 1: 1 ᅳ 1: 1.1, 1: 1.25 and 1: 1.5, respectively. PXRD pattern. FIG. 14 shows the nitrogen-adhesive isotherm of HKUST # 1 regenerated by reacting with a solution of the initial state HKUST-l, and nitric acid: NaOH = 1: 0.75, 1: 0.9, 1: 1, 1: 1.1 and 1: 1.25, respectively. to be.

도 15는 NaOH 용액의 첨가로부터 1분 뒤에 재생된 HKUST-l의 SEM 이미지이다ᅳ 도 16은 초기상태 HKUST-l, 및 NaOH 용액의 첨가로부터 1분 뒤에 재생된 HKUST-l의 IR스펙트럼이다.  FIG. 15 is an SEM image of HKUST-1 regenerated 1 minute after addition of NaOH solution. FIG. 16 is an IR spectrum of HKUST-1 regenerated after 1 minute from addition of NaOH solution.

도 17은 초기상태 HKUST-l, 및 NaOH 용액 첨가로부터 1분 후에 재생된 HKUST-l의 PXRD 패턴이다.  FIG. 17 is the PXRD pattern of initial state HKUST-1 and HKUST-1 regenerated 1 minute after addition of NaOH solution.

도 18은 초기상태 HKUST-lᅳ 및 NaOH 용액 첨가로부터 1분 후에 재생된 ffl(UST-l의 질소 흡착 등온선이다.  18 is a nitrogen adsorption isotherm of ffl (UST-l) regenerated 1 min after addition of the initial state of HKUST-l ᅳ and NaOH solution.

도 19는 서로 다른 4개의 손상된 HKUST-l 샘플의 흔합물로부터 재생된 HKUST-l의 SEM 이미지이다.  19 is an SEM image of HKUST-1 regenerated from a mixture of four different damaged HKUST-1 samples.

도 20은 초기상태 HKUST-l, 및 서로 다른 4개의 손상된 HKUST-l 샘플들의 흔합물로부터 재생된 HKUST-l의 IR스펙트럼이다.  20 is an IR spectrum of HKUST-l regenerated from a mixture of initial state HKUST-l and four different damaged HKUST-l samples.

도 21은 초기상태 HKUST-l, 및 서로 다른 4개의 손상된 HKUST-l 샘플들의 흔합물로부터 재생된 HKUST-l의 PXRD 패턴이다.  FIG. 21 is a PXRD pattern of HKUST-l regenerated from a mixture of initial HKUST-l and four different damaged HKUST-l samples.

도 22는 초기상태 HKUST-l, 및 서로 다른 4개의 손상된 HKUST-l 샘플들의 흔합물로부터 재생된 HKUST-1의 질소 흡착 등온선이다. FIG. 22 shows initial HKUST-l and four different damaged HKUST-l samples. Nitrogen adsorption isotherm of HKUST-1 regenerated from the mixture.

【발명의 실시를 위한 최선의 형태】 [Best form for implementation of the invention]

본 발명에 따른 금속 -유기 골격체의 재생방법은 (1) 손상된 금속 -유기 골격체 (M0F)를 산으로 처리하는 단계; 및 (2) 상기 산 처리된 금속 -유기 골격체를 아미드 처리하거나 염기 처리하여 재생하는 단계를 포함한다.  The method for regenerating a metal-organic framework according to the present invention comprises the steps of: (1) treating a damaged metal-organic framework (M0F) with an acid; And (2) regenerating the acid treated metal-organic framework by amide treatment or base treatment.

본 발명에 따르면 상기 단계들을 순차적으로 수행하거나 또는 동시에 수행할 수 있다. 동시에 수행할 경우, 상기 손상된 금속 -유기 골격체를 산으로 처리함과 동시에 아미드 처리 또는 염기 처리하여 재생할 수 있다.  According to the present invention, the above steps may be performed sequentially or simultaneously. When performed simultaneously, the damaged metal-organic framework can be regenerated by treatment with an acid and simultaneously with amide treatment or base treatment.

이하 각 단계별로 구체적으로 설명한다. 금속 -유기 골격체 본 발명에서 대상으로 하는 금속 -유기 골격체 (M0F)는 특별히 한정되지 않으며, 예를 들어 기공성을 갖는 금속 -유기 골격체일 수 있다.  Hereinafter, each step will be described in detail. Metal-Organic Framework The metal-organic framework (M0F) targeted in the present invention is not particularly limited, and may be, for example, a metal-organic framework having porosity.

구체적인 예로서， 상기 금속 -유기 골격체는 M0F-5( IRM0F-1) , HKUST-1 , IRMOF-2, IRMOF-3 , IRMOF-4, IRMOF-5, IRMOF-6 , IRMOF-7 , IRMOF-8 , IRMOF-9 , IRMOF-10 , IRMOF-ll , IRMOF-12 , IRMOF-13 , IRMOF-14, IRMOF-15, IRMOF-16, M0F- 74 (Mg) , M0F-74(Fe) , M0F-74(Co) , M0F-74(Ni ) , M0F-74(Zn) , MOF- 14, MOF- 177 , MOF— 508， UMCM-1 , DUT-9 , UiO-BPY , UiO-67 , ZrMOF-BIPY, UiO-68 , MOF-802, M0F- 804， MOF-805 , M0F-806 및 MOF-808로 이루어진 군으로부터 선택되는 적어도 하나를 포함할 수 있다. 상기 예시된 금속 -유기 골격체들의 구체적인 구조 (조성)는 아래와 같다: As a specific example, the metal-organic framework is M0F-5 (IRM0F-1), HKUST-1, IRMOF-2, IRMOF-3, IRMOF-4, IRMOF-5, IRMOF-6, IRMOF-7, IRMOF- 8, IRMOF-9, IRMOF-10, IRMOF-ll, IRMOF-12, IRMOF-13, IRMOF-14, IRMOF-15, IRMOF-16, M0F-74 (Mg), M0F-74 (Fe), M0F- 74 (Co), M0F-74 (Ni), M0F-74 (Zn), MOF-14, MOF-177, MOF—508, UMCM-1, DUT-9, UiO-BPY, UiO-67, ZrMOF-BIPY And UiO-68, MOF-802, MOF-804, MOF-805, MOF-806, and MOF-808. The specific structure (composition) of the metal-organic frameworks exemplified above is as follows:

- MOF-5 ( IRM0F-1) ： Zn40(BDC)3 -MOF-5 (IRM0F-1): Zn 4 0 (BDC) 3

- HKUST-1 ： (Cu3(BTC)2) -HKUST-1 ： (Cu 3 (BTC) 2)

- IRM0F-2 ： Zn40(BDC-Br)3 -IRM0F-2: Zn 4 0 (BDC-Br) 3

- IRM0F-3 ： Zn40(BDC-NH2)3 - IRMOF-4 ： Zn40(BDC-0C3H7)3 -IRM0F-3: Zn 4 0 (BDC-NH 2 ) 3 -IRMOF-4: Zn 4 0 (BDC-0C 3 H 7 ) 3

- IRMOF-5 ： Zn40(BDC-0C5Hn)3  IRMOF-5: Zn40 (BDC-0C5Hn) 3

- IRM0F-6 ： Zn40(BDC-C2H4)3 - IRM0F-6: Zn 4 0 (BDC-C 2 H 4) 3

― IRM0F-7 ： Zn40(BDOC4H4)3 IRM0F-7: Zn 4 0 (BDOC 4 H 4 ) 3

- I M0F-8 ： Zn40(2 , 6-NDC)3 -I M0F-8: Zn 4 0 (2, 6-NDC) 3

- IRM0F-9 ： Zn40(BPDC)3 ( interpenetrated)-IRM0F-9: Zn 4 0 (BPDC) 3 (interpenetrated)

- IRM0F-10 ： Zn40(BPDC)3 -IRM0F-10: Zn 4 0 (BPDC) 3

- IRM0F-11 ： Zn40(HPDC)3 ( interpenet rated)-IRM0F-11: Zn 4 0 (HPDC) 3 (interpenet rated)

- IRM0F-12 ： Zn40(HPDC)3 -IRM0F-12: Zn 4 0 (HPDC) 3

- IRM0F-13 ： Zn40(PDC)3 ( interpenetrated)-IRM0F-13 ： Zn 4 0 (PDC) 3 (interpenetrated)

- IRM0F-14 ： Zn40(PDC)3 -IRM0F-14: Zn 4 0 (PDC) 3

- IRM0F-15 ： Zn40(TPDC)3 ( interpenetrated)-IRM0F-15: Zn 4 0 (TPDC) 3 (interpenetrated)

- IRM0F-16 ： Zn40(TPDC)3 -IRM0F-16: Zn 4 0 (TPDC) 3

- M0F-74(Mg) (CP0-27-Mg) ： Mg2(D0BDC)-M0F-74 (Mg) (CP0-27-Mg): Mg 2 (D0BDC)

- M0F-74(Fe) (CP0-27-Fe) ： Fe2(D0BDC)-M0F-74 (Fe) (CP0-27-Fe): Fe 2 (D0BDC)

- M0F-74(Co) (CPO-27-Co) ： Co2(D0BDC)-M0F-74 (Co) (CPO-27-Co): Co 2 (D0BDC)

- M0F-74(Ni ) (CP0-27-Ni ) ： Ni2(D0BDC)-M0F-74 (Ni) (CP0-27-Ni): Ni 2 (D0BDC)

- M0F-74(Zn) (CP0-27-Zn) ： Zn2(D0BDC)M0F-74 (Zn) (CP0-27-Zn): Zn 2 (D0BDC)

- MOF-14 ： Cu3(BTB)2(¾0)3 -MOF-14: Cu 3 (BTB) 2 (¾0) 3

ᅳ MOF-177 ： Zn40(BTB)2 MOF-177: Zn 4 0 (BTB) 2

- MOF-508 ： Zn2(BDC)2(BPY) MOF-508: Zn 2 (BDC) 2 (BPY)

- UMCM-1 ： Zn40(BDC)3(BTB)4 -UMCM-1: Zn 4 0 (BDC) 3 (BTB) 4

- DUT-9 ： Ni502(BTB)2 -DUT-9: Ni 5 0 2 (BTB) 2

- UiO-BPY ： Zr606(BPY)i2 -UiO-BPY: Zr 6 0 6 (BPY) i 2

- UiO-67 ： Zr606(BPDC)i2 -UiO-67: Zr 6 0 6 (BPDC) i2

- ZrMOF-BIPY ： Zr606(BIPY)i2 -ZrMOF-BIPY: Zr 6 0 6 (BIPY) i 2

- UiO-68 ： Zr606(TPDC)i2 -UiO-68 ： Zr 6 0 6 (TPDC) i2

- MOF-802 ： Zr604(()H)4(PZDC)5(HC0())2(¾())2 - MOF-804 Zr604(0H)4[BDC-(0H)2]6 -MOF-802: Zr 6 0 4 (() H) 4 (PZDC) 5 (HC0 ()) 2 (¾ ()) 2 -MOF-804 Zr 6 0 4 (0H) 4 [BDC- (0H) 2 ] 6

- MOF-805 Zr604(0H)4[NDC-(0H)2]6 -MOF-805 Zr 6 0 4 (0H) 4 [NDC- (0H) 2 ] 6

- MOF-806 Zr604(0H)4[BPDC-(0H)2]6 -MOF-806 Zr 6 0 4 (0H) 4 [BPDC- (0H) 2 ] 6

- M0F-808 Zr604(0H)4(BTC)2[HC00]6 -M0F-808 Zr 6 0 4 (0H) 4 (BTC) 2 [HC00] 6

또한， 상기 조성에 기재된 약어의 의미는 아래와 같다: In addition, the meaning of the abbreviations described in the above composition is as follows:

- BDC ： 1 , 4-benzenedi carboxy 1 ate  -BDC: 1, 4-benzenedi carboxy 1 ate

- BTC ： 1,3, 5-benzenet r i car boxy 1 at e  -BTC: 1,3, 5-benzenet r i car boxy 1 at e

- BDC-Br ： 2-bromo-l , -benzenedi carboxy 1 at e  -BDC-Br: 2-bromo-l, -benzenedi carboxy 1 at e

- BDC-NH2 ： 2-amino-l , 4-benzenedi carboxy 1 at e  -BDC-NH2: 2-amino-l, 4-benzenedi carboxy 1 at e

- BDC-OC3H7 ： 2 , 5-d i ropoxy- 1 , 4-benzened i carboxy late  -BDC-OC3H7: 2, 5-d i ropoxy-1, 4-benzened i carboxy late

- BDC—OCeHn ： 2 , 5-b i s (pent y 1 oxy ) - 1 , 4-benzened i car boxy late -BDC—OCeHn: 2, 5-b i s (pent y 1 oxy)-1, 4-benzened i car boxy late

- BDC-C2H4 ： b i eye lo[4.2.0]octa-l,3,5-tri ene~2 , 5-d i carboxy 1 at e-BDC-C2H4: bi eye lo [4.2.0] octa-l, 3,5-triene ~ 2, 5-di carboxy 1 at e

- BDC-C4H4 ： 1 , 4-naphtha 1 enedi carboxy 1 at e -BDC-C4H4: 1, 4-naphtha 1 enedi carboxy 1 at e

- 2 , 6-NDC ： 2, 6ᅳ naphtha 1 enedi carboxy late  -2, 6-NDC: 2, 6 ᅳ naphtha 1 enedi carboxy late

ᅳ BPDC ： 4 , 4 ' -b i heny 1 -d i carboxy late ᅳ BPDC ： 4, 4 '-b i heny 1 -d i carboxy late

- HPDC ： 4,5,9, 10-t et r ahydropyr ene-2 , 7-d i carboxy 1 at e  -HPDC ： 4,5,9, 10-t et r ahydropyr ene-2, 7-d i carboxy 1 at e

ᅳ PDC ： pyridine-2, 5-di car boxy late ᅳ PDC ： pyridine-2, 5-di car boxy late

- TPDC ： ter henyl di car boxy late  -TPDC: ter henyl di car boxy late

- DOBDC ： 2 , 5-d i hydr oxy t er epht ha 1 at e  -DOBDC: 2, 5-d i hydr oxy t er epht ha 1 at e

- BTB ： 4,4' ,4' '-benzene-l,3,5-triyl-tribenzoate  -BTB: 4,4 ', 4' '-benzene-l, 3,5-triyl-tribenzoate

- BPY ： 4,4'-bipyridine  -BPY ： 4,4'-bipyridine

- BIPY ： 2,2' -bipyri dine-5, 5' -di carboxy late  -BIPY: 2,2 '-bipyri dine-5, 5' -di carboxy late

- PZDC ： lff-pyr azo 1 e~3 , 5-d i carboxy 1 at e -PZDC: lff-pyr azo 1 e ~ 3, 5-di carboxy 1 at e

ᅳ BDC- (OH )2： 2 , 5-d i hydroxy- 1 , 4-benzened i carboxy 1 at e DC BDC- (OH) 2: 2, 5-d i hydroxy- 1, 4-benzened i carboxy 1 at e

- NDCᅳ (0H)2 1 , 5-d i hydr oxynapht ha 1 ene-2 , 6-di carboxy 1 at e ᅳ BPDC- (OH )2 : 3 , 3 ' -d i hydr oxy-4 , 4 ' -b i hen 1 d i carboxy late 손상된 금속 -유기 골격체 본 발명의 방법에 따르면， 손상된 금속 -유기 골격체를 재생한다 . -NDC ᅳ (0H) 2 1, 5-di hydr oxynapht ha 1 ene-2, 6-di carboxy 1 at e ᅳ BPDC- (OH) 2: 3, 3 '-di hydr oxy-4, 4' -bi hen 1 di carboxy late Damaged Metal-Organic Skeletal According to the method of the present invention, a damaged metal-organic framework is regenerated.

구체적으로， 상기 손상된 금속 -유기 골격체는 앞서 예시한 다양한 금속- 유기 골격체들 중 적어도 하나가 손상된 것일 수 있다.  Specifically, the damaged metal-organic framework may be at least one of the various metal-organic frameworks exemplified above.

상기 손상된 금속 -유기 골격체는 분해 혹은 퇴화 (degradat ion)되거나， 또는 변질 혹은 훼손 (deter iorat ion)된 금속 -유기 골격체를 의미한다.  The damaged metal-organic framework refers to a metal-organic framework that has been degraded or degraded, or deteriorated or deteriorated.

상기 손상된 금속 -유기 골격체는 물, 증기， 염산， 질산, 황산 인산， 아세트산， 수산화나트륨 수용액， 수산화칼륨 수용액， 아세톤， 사염화탄소， 클로로포름， 디클로로메테인， 디메틸아세트아미드， 디에틸포름아미드， 디메틸설폭사이드, 벤젠， 를루엔， 메탄올， 에탄을， 프로판올， 이소프로필알콜 등에 의해 손상된 금속 -유기 골격체를 포함할 수 있다. 바람직하게는， 상기 손상된 금속 -유기 골격체는 물 또는 증기에 의해 손상된 금속 -유기 골격체를 포함할 수 있다.  The damaged metal-organic framework is water, steam, hydrochloric acid, nitric acid, sulfuric acid phosphoric acid, acetic acid, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, acetone, carbon tetrachloride, chloroform, dichloromethane, dimethylacetamide, diethylformamide, dimethyl sulfoxide And metal-organic frameworks damaged by sides, benzene, toluene, methanol, ethane, propanol, isopropyl alcohol and the like. Preferably, the damaged metal-organic framework may comprise a metal-organic framework damaged by water or steam.

또한， 상기 손상된 금속—유기 골격체는， 원료로부터 합성된 직후의 초기상태의 금속 -유기 골격체에 비해， 기공도 및 /또는 BET 비표면적이 99% 이하， 90% 이하， 80% 이하， 또는 70% 이하인 금속 -유기 골격체를 의미할 수 있다. 산처리 본 단계는 상기 손상된 금속 -유기 골격체 (M0F)를 산으로 처리하는 단계이다.  In addition, the damaged metal-organic framework has a porosity and / or BET specific surface area of 99% or less, 90% or less, 80% or less, compared to the metal-organic framework in its initial state immediately after synthesis from the raw material. It can mean a metal-organic framework that is 70% or less. Acid Treatment This step is a step of treating the damaged metal-organic framework (M0F) with an acid.

본 단계에서 사용되는 산의 종류는 특별히 한정되지 않으나， 강산인 것이 바람직하다. 예를 들어， 상기 산으로서 질산 (HN03) , 염산 (HC1 ) , 아세트산， 포름산， 불화수소산 등을 사용할 수 있다. The type of acid used in this step is not particularly limited, but is preferably a strong acid. For example, nitric acid (HN0 3 ), hydrochloric acid (HC1), acetic acid, formic acid, hydrofluoric acid and the like can be used as the acid.

금속 -유기 골격체는 일반적으로 카르복시기가 포함된 리간드로 구성되므로 산에 약하며， 물에 의해 손상된 금속 -유기 골격체 또한 금속 이온과 카르복시기가 포함된 리간드로 구성되어 있어서 강산을 첨가하여 쉽게 녹일 수 있다. 손상된 금속 -유기 골격체는 손상되기 전의 금속 -유기 골격체와 동일한 화학량적인 비 (stoichiometric ratio)의 금속 이온과 리간드를 함유하고 있으므로, 이를 산과 유기용매를 처리하여 녹이게 되면 기존 금속 -유기 골격체 합성에 필요한 용액과 비슷한 조건이 된다. The metal-organic framework is generally weak to acids because it is composed of ligands containing carboxyl groups, and the metal-organic frameworks damaged by water are also composed of ligands containing metal ions and carboxyl groups and can be easily dissolved by addition of strong acids. . Damaged metal-organic frameworks contain the same stoichiometric ratios of metal ions and ligands as the metal-organic frameworks before they are damaged. Conditions similar to those required for synthesis.

산 처리는 용매 중에서 수행될 수 있으며, 예를 들어 상기 손상된 금속- 유기 골격체에 용매 및 /또는 산을 가하여 수행될 수 있다.  The acid treatment can be carried out in a solvent, for example by adding a solvent and / or an acid to the damaged metal-organic framework.

구체적으로， 상기 산 처리는 상기 손상된 금속 -유기 골격체를 d-3알콜， 물， 디메틸포름아미드， 아세톤， 사염화탄소, 클로로포름， 다이클로로메테인， 디메틸아세트아미드， 디에틸포름아미드, 디메틸설폭사이드, 벤젠, 를루엔， 또는 이들의 흔합 용매 중에서 교반시킴으로써 수행될 수 있다. 염기 조건 반웅 (재생 반웅) 본 단계는 앞서 산 처리된 금속 -유기 골격체를 아미드 처리하거나 염기 처리하여 재생하는 단계이다. Specifically, the acid treatment is performed by treating the damaged metal-organic framework with d- 3 alcohol, water, dimethylformamide, acetone, carbon tetrachloride, chloroform, dichloromethane, dimethylacetamide, diethylformamide, dimethylsulfoxide, It may be carried out by stirring in benzene, toluene, or a mixed solvent thereof. Base conditions reaction (regeneration reaction) This step is a step of regenerating the acid-treated metal-organic framework by amide treatment or base treatment.

상기 재생 단계는 (i) 내부 염기 생성 (즉 in situ 경로) 또는 (ii) 외부 염기 첨가 (즉 ex situ경로)의 2가지 경로로 형성될 수 있다. 내부 염기 생성을 통한 재생 반응  The regeneration step can be formed in two ways: (i) internal base production (ie in situ pathway) or (ii) external base addition (ie ex situ pathway). Regeneration reaction through internal base generation

상기 아미드 처리하여 재생하는 단계는 상기 산 처리된 금속 -유기 골격체를 60 내지 150°C의 온도 조건 하에 아미드계 용매 중에서 교반시키는 것을 포함할 수 있다. 또한 상기 아미드 처리 시의 반웅 온도는 보다 한정할 경우 70 내지 120 °C일 수 있다. The regenerating step by treating with amide may include stirring the acid treated metal-organic framework in an amide solvent under a temperature condition of 60 to 150 ° C. In addition, the reaction temperature during the amide treatment may be 70 to 120 ° C if more limited.

상기 아미드 처리하여 재생하는 단계는 상기 아미드 처리를 통해 자체적으로 내부에 염기가 생성 (/ situ base generation)될 수 있다. 상기 아미드 처리하여 재생하는 단계는 용매열 반웅 (solvothermal reaction)을 포함할 수 있다.  Regeneration by the amide treatment may be a base (/ situ base generation) in itself through the amide treatment. The regeneration by treating the amide may include a solvothermal reaction.

상기 아미드계 용매는 디에틸포름아미드 (DEF;N,N'-diethylformamide), 디메틸포름아미드 (DMF ;N ,N ' -dimethyl formamide) , 또는 이들의 흔합 용매를 포함할 수 있다. The amide solvent is diethylformamide (DEF; N, N'-diethylformamide), Dimethylformamide (DMF; N, N'-dimethyl formamide), or a mixed solvent thereof.

상기 아미드 용매의 처리 전 pH 조건은 pH 4 내지 14 , 구체적으로 pH 4 내지 12， 보다 구체적으로 pH 4 내지 10의 범위의 조건일 수 있다.  The pH condition before the treatment of the amide solvent may be in the range of pH 4 to 14, specifically pH 4 to 12, more specifically pH 4 to 10.

구체적인 일례에 따르면 상기 금속 -유기 골격체는 MOF-5 , HKUST-1 또는 이들의 흔합물을 포함하고， 상기 아미드 처리는 상기 산 처리된 금속—유기 골격체를 60 내지 150°C의 온도 하에 아미드계 용매 중에서 교반시키는 것을 포함할 수 있다. According to a specific example the metal-organic framework comprises MOF-5, HKUST-1 or a combination thereof, and the amide treatment results in the amide treatment of the acid treated metal—organic framework at a temperature of 60 to 150 ° C. It may include stirring in a system solvent.

다른 예에 따르면， 상기 아미드 처리는 앞서의 산 처리 단계와 동시에 수행될 수 있다. 예를 들어， 상기 방법은 손상된 금속—유기 골격체에 산 및 아미드계 용매를 동시에 가한 뒤 60 내지 150 °C의 온도로 용매열 반응시켜 수행될 수 있다. 외부 염기 첨가를 통한 재생 반웅 According to another example, the amide treatment can be carried out simultaneously with the acid treatment step above. For example, the process can be carried out by simultaneous addition of acid and amide solvents to the damaged metal—organic framework followed by solvent thermal reaction at a temperature of 60 to 150 ° C. Regeneration reaction by addition of external base

상기 염기 처리하여 재생하는 단계는 상기 산 처리된 금속 -유기 골격체를 상온 조건 하에 염기성 용매 중에서 교반시키는 것을 포함할 수 있다.  Regenerating by treating the base may include stirring the acid-treated metal-organic framework in a basic solvent under room temperature conditions.

상기 염기성 용매는 상기 산 1 당량에 대해서 0.75 내지 1.25 당량， 0.75 내지 1. 1 당량， 0.9 내지 1. 1 당량의 양으로 첨가될 수 있다. 또는， 상기 염기성 용매는 상기 산 1 당량에 대해서 0.75 내지 1 당량의 양으로 첨가될 수 있다. 여기서 산 1 당량에 대해서 염기 1 당량이라고 하면， 산 1 몰의 양을 중화시킬 수 있는 염기의 몰수에 해당하는 양을 의미한다.  The basic solvent may be added in an amount of 0.75 to 1.25 equivalents, 0.75 to 1.1 equivalents, and 0.9 to 1.1 equivalents based on 1 equivalent of the acid. Alternatively, the basic solvent may be added in an amount of 0.75 to 1 equivalent based on 1 equivalent of the acid. Here, 1 equivalent of base to 1 equivalent of acid means an amount corresponding to the number of moles of base that can neutralize the amount of 1 mole of acid.

상기 염기성 용매는 수산화나트륨 (NaOH) 수용액, 수산화칼륨 (K0H) 수용액， 또는 이들의 혼합 용매를 포함할 수 있다.  The basic solvent may include an aqueous sodium hydroxide (NaOH) solution, an aqueous potassium hydroxide (K0H) solution, or a mixed solvent thereof.

구체적인 일례에 따르면， 상기 금속 -유기 골격체는 HKUST-1를 포함하고， 상기 염기 처리는 상기 산 처리된 금속 -유기 골격체를 상온 조건 하에 염기성 용매 중에서 교반시키는 것을 포함할 수 있다.  According to a specific example, the metal-organic framework includes HKUST-1, and the base treatment may include stirring the acid treated metal-organic framework in a basic solvent under room temperature conditions.

비화학량론적 재생 반웅 또한, 상기 재생 반웅은 금속과 리간드의 비율 면에서 비화학량론적 (non- stoi chiometr i c) 반웅이어도 가능하다. Nonstoichiometric Reaction In addition, the regeneration reaction may be a non-stoichiometric reaction in terms of the ratio of metal and ligand.

따라서， 상기 재생 반웅， 즉, 상기 아미드 처리 또는 염기 처리는 상기 산 처리된 금속 -유기 골격체에 금속 이온을 더 첨가한 이후에, 앞서의 in s i tu 또는 ex s i tu 경로로 수행될 수 있다.  Thus, the regeneration reaction, i.e., the amide treatment or the base treatment can be carried out in the above in s i tu or ex s i tu route after further addition of metal ions to the acid treated metal-organic framework.

또한， 상기 재생 반응은 앞서의 산 처리 단계와 동시에 수행될 수 있으며， 이 경우 손상된 금속 -유기 골격체에 산, 금속 이온， 및 용매 (아미드계 용매 또는 염기성 용매)가 동시에 가해진 후에 재생 반웅이 수행될 수 있다.  In addition, the regeneration reaction may be carried out simultaneously with the acid treatment step, in which case the regeneration reaction is performed after an acid, a metal ion, and a solvent (amide based solvent or basic solvent) are simultaneously added to the damaged metal-organic framework. Can be.

상기 금속 이온의 종류로는 재생하려는 금속 -유기 골격체를 구성할 수 있는 금속 이온이라면 특별히 한정되지 않는다. 예를 들어， HKUST-1의 재생 반응에는 Cu( I I ) 이온을 추가로 첨가하여 반응을 수행할 수 있다.  The kind of metal ion is not particularly limited as long as it is a metal ion capable of constituting a metal-organic skeleton to be regenerated. For example, in the regeneration reaction of HKUST-1, the reaction may be performed by further adding Cu (I I) ions.

상기 금속 이온의 첨가량은 특별히 한정되지 않으나, 예를 들어 상기 산 처리된 금속 -유기 골격체 용액에 함유된 금속 이온의 몰수의 1 내지 50%ᅳ 10 내지 40%, 또는 1 내지 30%에 해당하는 몰수의 금속 이온을 첨가할 수 있다. 재생된 금속 -유기 골격체 이상의 단계를 거쳐 재생된 금속 -유기 골격체는， 손상되기 이전의 금속- 유기 골격체 (원료로부터 합성된 직후의 초기상태의 금속 -유기 골격체)에 대비하여, 90% 이상의 기공도 및 BET 비표면적을 회복할 수 있다.  The addition amount of the metal ions is not particularly limited, but for example, 1 to 50% ᅳ 10 to 40%, or 1 to 30% of the number of moles of metal ions contained in the acid-treated metal-organic framework solution Moles of metal ions can be added. Regenerated Metal-Organic Skeletal The regenerated metal-organic framework, which has undergone more than one step, is prepared in contrast to the metal-organic framework before damage (the initial metal-organic framework just after synthesis from the raw material). Porosity and BET specific surface area of more than% can be recovered.

구체적으로， 상기 재생된 금속 -유기 골격체는， 손상 이전의 금속—유기 골격체에 대비하여， 90% 이상， 95% 이상， 나아가 98% 이상의 기공도를 회복할 수 있다.  Specifically, the regenerated metal-organic framework can recover porosity of at least 90%, at least 95% and even at least 98% relative to the metal-organic framework prior to damage.

또한， 상기 재생된 금속 -유기 골격체는, 손상 이전의 금속 -유기 골격체에 대비하여, 90% 이상， 95% 이상， 나아가 98% 이상의 BET 비표면적을 회복할 수 있다.  In addition, the regenerated metal-organic framework can recover a BET specific surface area of at least 90%, at least 95%, and at least 98%, relative to the metal-organic framework prior to damage.

【발명의 실시를 위한 형태】  [Form for implementation of invention]

이하， 본 발명을 실시예에 의해 보다 상세히 설명한다. 단 하기 실시예는 본 발명을 예시하는 것일 뿐， 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다ᅳ Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples It is merely to illustrate the invention, but the content of the invention is not limited to the following examples ᅳ

재료 및 방법 Materials and methods

시료 화합물들은 시판하는 제품을 구매하여 별도의 정제없이 사용하였다. Sample compounds were purchased without commercial purification.

Ζη(Ν03)2·6Η20, 1，4-벤젠디카복실산 (H2BDC：)， 무수 DMF, 무수 메틸클로라이드 (MC), 질산, 염산 및 수산화나트륨 수용액은 Sigma- Aldrich사로부터 구매하였다. Ζη (Ν0 3 ) 2 · 6Η 2 0, 1,4-benzenedicarboxylic acid (H 2 BDC :), anhydrous DMF, anhydrous methyl chloride (MC), nitric acid, hydrochloric acid and sodium hydroxide aqueous solution were purchased from Sigma-Aldrich. .

DEF는 TCI사로부터 구매하였다.  DEF was purchased from TCI.

에탄올은 B&J사로부터 구매하였다.  Ethanol was purchased from B & J.

시판하는 HKUST-1인 Basolite C300은 BASF사로부터 구매하였다.  Commercially available HKUST-1, Basolite C300, was purchased from BASF.

분말 X선 회절분석 (PXRD)은 Bruker D2 PHASER를 이용하여 수행되었다. 적외선스펙트럼 (IR)은 ThermoFisher Scientifc iS10 FT—IR 분광기를 이용하여 측정되었다.  Powder X-ray diffraction (PXRD) was performed using Bruker D2 PHASER. Infrared spectra (IR) were measured using a ThermoFisher Scientifc iS10 FT—IR spectrometer.

전계방출 주사전자현미경 (SEM) 이미지는 FEI Nova NanoSEM 230을 사용하여 관찰되었다.  Field emission scanning electron microscopy (SEM) images were observed using a FEI Nova NanoSEM 230.

질소 흡착 등온선은 77K에서 ASAP 2020 (Micromer it ics Instrument Corporation사)을 이용하여 표준용적측정기술 (standard volumetric technique)에 따라 최대 1기압의 조건으로 측정되었다. 제조예 1: 금속 -유기 골격체의 제조  Nitrogen adsorption isotherms were measured at 77 K under conditions of up to 1 atmosphere using ASAP 2020 (Micromer itics Instrument Corporation) according to standard volumetric techniques. Preparation Example 1 Preparation of Metal-Organic Framework

(1-1) M0F-5의 제조 (1-1) Preparation of M0F-5

Zn(N03)2-6H20 0.75g (2.5匪 ol) 및 1 ,4-벤젠디카복실산 (H2BDC) 0.20g (1.2隱01)을 DEF 50mL와 함께 125mL 용기에 넣었다. 반웅용액을 100°C 오본에서 2일 동안 가열하였다. 반응액을 상온으로 식힌 후 용매를 제거하였다. 결정형의 생성물을 무수 DMF 및 무수 MC로 수회 세척하였다. 생성물을 150°C 진공 오븐에서 밤새 건조하였다 (0.28g, 수율 = 91%) . (1-2) HKUST-1의 제조 Zn (N0 3) 2 -6H 2 0 were added to 0.75g (2.5匪ol) and 1, 4-benzene dicarboxylic acid (H 2 BDC) 0.20g (1.2隱0 1) in 125mL vessel with 50mL DEF. The reaction solution was heated at 100 ° C. Aubon for 2 days. After cooling the reaction solution to room temperature, the solvent was removed. The crystalline product was washed several times with anhydrous DMF and anhydrous MC. The product was dried overnight in a 150 ° C. vacuum oven (0.28 g, yield = 91%). (1-2) Manufacture of HKUST-1

종래 기술 (S. Xiang et al . , J. Am. Chem. Soc. 2009， 131, 12415.)에 따라 HKUST-1을 제조하였다. 제조예 2: 손상된 금속 -유기 골격체의 제조  HKUST-1 was prepared according to the prior art (S. Xiang et al., J. Am. Chem. Soc. 2009, 131, 12415.). Preparation Example 2 Preparation of Damaged Metal-Organic Skeletal

(2-1) 손상된 M0F-5의 제조 (2-1) Preparation of Damaged M0F-5

앞서의 제조예 1-1에서 제조된 MOF-5 0.25g을 증류수 50mL에 침지하고， 1일간 교반하였다. 손상된 샘플을 60°C 오븐에서 완전히 건조시켰다. 0.25 g of MOF-5 prepared in Preparation Example 1-1 was immersed in 50 mL of distilled water and stirred for 1 day. The damaged sample was completely dried in a 60 ° C. oven.

(2-2) 손상된 HKUST-1의 제조 (2-2) Preparation of Damaged HKUST-1

HKUST-KBasolite C300, BASF사) lg에 물 50mL를 가하고， 대기 조건에서 1일간 교반하였다. 손상된 샘플을 100°C 오븐에서 완전히 건조시켰다. 50 mL of water was added to lg HKUST-KBasolite C300, BASF Co., Ltd., and the mixture was stirred for 1 day at atmospheric conditions. The damaged sample was completely dried in a 100 ° C oven.

(2-3) 서로 다른 HKUST— 1 손상 샘플들의 흔합물 (2-3) Mixture of Different HKUST— 1 Damage Samples

2종의 원료 물질 (앞서 제조된 손상된 HKUST-1 및 초기상태 HKUST-1)을 이용하여 2가지의 경로를 통해， 총 4개의 서로 다른 HKUST-1 손상 샘플을 제조하였다. 구체적으로， 손상된 HKUST-1 또는 초기상태 HKUST-1 2g에 물 80mL를 가하고， (경로 1) 대기 조건에서 1일간 교반하거나， (경로 2) 100°C에서 6시간 동안 교반하였다. 수득된 4종의 손상 샘플들을 100°C 오븐에서 밤새 건조하여 손상 샘플들의 흔합물을 얻었다. 실시예 1: 내부 염기 생성을 통한 M0F-5의 재생 A total of four different HKUST-1 damaged samples were prepared via two routes using two raw materials (previously damaged HKUST-1 and initial HKUST-1). Specifically, 80 mL of water was added to 2 g of damaged HKUST-1 or initial state HKUST-1, and stirred for 1 day at atmospheric conditions (path 1), or for 6 hours at 100 ° C. (path 2). The four damaged samples obtained were dried overnight in a 100 ° C. oven to obtain a mixture of damaged samples. Example 1: Regeneration of M0F-5 via Internal Base Generation

70% 농도의 질산 용액 0.2mL를 DEF 50mL와 흔합한 용액을 제조하고， 여기에 상기 제조예 2-1에서 얻은 손상된 MOF-5 0.25g을 녹였다. 반웅 용액을 .수 분간 초음파 처리하고 10C C 오본에서 2일 동안 보관하였다. 샘플 내의 용매를 2일 동안 DMF 및 MC로 각각 5회 교체해주었다. 샘플을 150°C의 진공 조건에서 밤새 건조하였다 (0.22g, 수율 = 85%) . 실시예 2: 내부 염기 생성을 통한 HKUST-1의 재생 상기 제조예 2-2에서 얻은 손상된 HKUST-1 l.OOg에， 1M 질산 용액 또는 1M 염산 용액 lOmL, 및 DMF/EtOH/¾0 (2:2:1, v/v/v) 50mL을 가하면서 교반하였다. 반웅 용액을 70°C 오본에서 1일간 보관하였다. 용매를 DMF 및 아세톤으로 2일 동안 수회 교체해주었다. 샘플을 120°C의 진공 조건에서 1일간 건조하였다. 재생 수율은， 질산을 첨가한 경우 0.87g(87%)이었고， 염산을 첨가한 경우에는 0.70g(70%)이었다. 실시예 3: 외부 염기 첨가를 통한 HKUST-1의 재생 상기 제조예 2-2에서 얻은 손상된 HKUST-1 l.OOg에 , 1M 염산 용액 20mL 및 EtOH/H20 (1:1， v/v) 80mL을 가하면서 교반하였다. 반웅 용액에 1M NaOH 용액 10mL, 20mL 및 25niL (각각 산 -염기 비율로서 1:0.75， 1:1 및 1:1.25 에 해당)의 양으로 가하여 침전물을 즉시 형성하였다. 추가 1시간 동안 용매를 더 교반하고, 침전물을 여과한 후 에탄을로 수회 세척하였다. 생성물을 120°C의 진공 조건에서 밤새 건조하였다 (재생 수율 → HC1 ： NaOH = 1:0.75 (0.38 g, 38%) , 1:1 (0.87 g, 87%)， 및 1:1.25 (0.63 g, 63%)). 실시예 4: 서로 다른손상 샘플들의 흔합물로부터의 HKUST-1 재생 상기 제조예 2-3에서 얻은 손상 샘플들의 흔합물 8.0g을 1M HC1 용액0.2 mL of a 70% nitric acid solution was prepared with 50 mL of DEF, and 0.25 g of the damaged MOF-5 obtained in Preparation Example 2-1 was dissolved therein. The reaction solution was sonicated for several minutes and stored for 2 days in 10C C Aubon. Solvent in the sample Five replacements were made with DMF and MC each for 2 days. Samples were dried overnight under vacuum at 150 ° C. (0.22 g, yield = 85%). Example 2 Regeneration of HKUST-1 Through Internal Base Production Into the damaged HKUST-1 l.OOg obtained in Preparation Example 2-2, lOmL of 1M nitric acid solution or 1M hydrochloric acid solution, and DMF / EtOH / ¾0 (2: 2 : 1, v / v / v) 50mL was added stirring. The reaction solution was stored for 1 day at 70 ° C. Obon. The solvent was replaced several times for 2 days with DMF and acetone. Samples were dried for 1 day at 120 ° C. in vacuum. The recovery yield was 0.87 g (87%) with nitric acid and 0.70 g (70%) with hydrochloric acid. Example 3: Regeneration of HKUST-1 through Addition of External Base Into the damaged HKUST-1 l.OOg obtained in Preparation Example 2-2, 20 mL of 1M hydrochloric acid solution and EtOH / H 2 0 (1: 1, v / v) Stirring adding 80 mL. To the reaction solution was added 10 mL, 20 mL and 25 niL of 1M NaOH solution (corresponding to 1: 0.75, 1: 1 and 1: 1.25 as acid-base ratios respectively) to form a precipitate immediately. The solvent is further stirred for an additional 1 hour, the precipitate is filtered off and washed several times with ethane. The product was dried overnight under vacuum at 120 ° C. (regeneration yield → HC1: NaOH = 1: 0.75 (0.38 g, 38%), 1: 1 (0.87 g, 87%), and 1: 1.25 (0.63 g, 63%)). Example 4 HKUST-1 Regeneration from Mixtures of Different Damage Samples 8.0 g of the mixture of damaged samples obtained in Preparation Example 2-3 was prepared using a 1M HC1 solution.

140mL에 녹이고， 여기에 EtOH/H20 흔합 용매 (1:1， v/v) 160mL를 가한 뒤 교반하였다. 미량의 미용해된 고체 (약 lmg 미만)를 제거한 후, 1M NaOH 용액It was dissolved in 140mL, and after adding 160mL of EtOH / H 2 0 mixed solvent (1: 1, v / v), it was stirred. 1 M NaOH solution after removal of trace undissolved solids (less than about lmg)

140mL를 천천히 가하고 5분간 교반하였다. 1시간 더 교반한 후， 침전물을 여과하고 에탄을로 수회 세척한 후， 120 °C 진공 조건에서 밤새 건조하였다 (7.4g , 재생 수율 = 93%) . 시험예 1 : 내부 염기 생성을 통해 재생된 M0F-5의 분석 앞서의 실시예 1에서， 손상된 M0F-5 샘플을 질산 용액에 용해하고 DEF와의 용매열 반웅을 통해 M0F-5를 초기상태로 재생하였다. 140 mL was slowly added and stirred for 5 minutes. After one more hour of stirring, the precipitate After filtration and washing with ethane several times, it was dried overnight at 120 ° C. in vacuum (7.4 g, regeneration yield = 93%). Test Example 1 Analysis of Regenerated M0F-5 Through Internal Base Production In Example 1 above, the damaged M0F-5 sample was dissolved in nitric acid solution and M0F-5 was regenerated to the initial state through solvent heat reaction with DEF. .

도 5는 (a) 합성직후의 MOF-5 , (b) 손상된 M0F-5 , 및 (c) 재생된 M0F-5의 SEM 이미지를 나타낸다. 도 2a 및 도 6는 재생된 M0F-5의 PXRD 패턴 및 IR 스펙트럼이며， 이를 볼 때， 손상된 M0F가 초기상태의 M0F-5로 재생되었음을 알 수 있다. 실시예 1에서의 재생 수율은 85%로 확인되었으며， 이는 원료 물질로부터 M0F-5를 합성시의 수율 (91%)에 비견할만하다. 도 2b는 재생된 M0F-5의 질소 흡착 거동을 나타내며, 이를 통해 기공도가 완전히 회복되었음을 알 수 있다. 또한, 재생된 M0F-5의 BET 비표면적 (3480 m2/g)은 원료물질로부터 합성된 직후의 M0F- 5의 BET 비표면적 (3520 m2/g)에 비견할만하다 . 시험예 2 : 내부 염기 생성을 통해 재생된 HKUST-1의 분석 앞서의 실시예 2에서는， 손상된 HKUST-1을 강산 용액에 녹인 후， DMF/EtOH/¾0의 흔합 용매 중에서 용매열 반응시켜 마이크로미터 사이즈의 HKUST- 1 결정을 얻었다 (도 3 및 도 7 및 8 참조) . Figure 5 shows SEM images of (a) MOF-5 immediately after synthesis, (b) damaged M0F-5, and (c) regenerated M0F-5. 2A and 6 are PXRD patterns and IR spectra of regenerated M0F-5, and it can be seen that damaged M0F is regenerated to initial state M0F-5. The recovery yield in Example 1 was found to be 85%, which is comparable to the yield (91%) when synthesizing M0F-5 from raw materials. Figure 2b shows the nitrogen adsorption behavior of the regenerated M0F-5, it can be seen that the porosity was recovered completely. In addition, the BET specific surface area (3480 m 2 / g) of regenerated M0F-5 is comparable to the BET specific surface area (3520 m 2 / g) of M0F-5 immediately after synthesis from the raw materials. Test Example 2 Analysis of HKUST-1 Regenerated by Internal Base Production In Example 2, the damaged HKUST-1 was dissolved in a strong acid solution and then subjected to solvent thermal reaction in a mixed solvent of DMF / EtOH / ¾0 to measure the micrometer size. HKUST-1 crystals were obtained (see FIGS. 3 and 7 and 8).

금속 -유기 골격체의 구조적 특성뿐만 아니라 기공도 면에서도， 내부의 염기 소스인 DMF 함유 용액 중에서 용매열 반웅을 통해 회복되었다. 재생된 In terms of the porosity as well as the structural properties of the metal-organic framework, it was recovered through solvent heat reaction in a solution containing DMF, the internal base source. Recycled

HKUST-1의 질소 흡착 등은선은 초기상태 HKUST-1와 동일하였다 (도 9 참조) . 질산 또는 염산을 함유하는 용액으로 처리된 후 재생된 HKUST-1 샘플의 BET 비표면적 ( 1820 또는 1840 m2/g)은 초기상태 HKUST-1의 비표면적 ( 1840 m2/g)과 동일하였다. 회복 수율 면에서는 산의 종류에 따라 약간의 차이가 나타났으며, 구체적으로 질산 처리된 HKUST-1의 회복 수율이 약 9OT에 달하는 한편， 염산 처리된 HKUST-1의 회복 수율은 약 70%로 확인되었다. 시험예 3: 외부 염기 첨가를 통해 재생된 HKUST-1의 분석 앞서의 실시예 3에서는， 손상된 HKUST-1을 강산 용액으로 처리한 후， 아미드계 용매를 사용하지 않고도, 단지 염기晕 외부에서 첨가하여 네트워크 구조 형성에 적합한 pH로 조절함으로써 손상된 HKUST-1을 재생하였다. Nitrogen adsorption, etc. of HKUST-1 was the same as the initial state HKUST-1 (see Fig. 9). After treatment with a solution containing nitric acid or hydrochloric acid, the BET specific surface area of the reproduced HKUST-1 samples (1820 or 1840 m 2 / g) was the same as the specific surface area of the initial state HKUST-1 (1840 m 2 / g). In terms of recovery yield, there was a slight difference depending on the type of acid. Specifically, the recovery yield of nitric acid treated HKUST-1 reached about 9OT, and hydrochloric acid. The recovery yield of treated HKUST-1 was found to be about 70%. Test Example 3 Analysis of HKUST-1 Regenerated by External Base Addition In Example 3, after treating damaged HKUST-1 with a strong acid solution, it was added only outside the base, without using an amide solvent. Damaged HKUST-1 was regenerated by adjusting to a pH suitable for network structure formation.

외부 염기 첨가에 의해 재생된 HKUST-1의 IR 스펙트럼은 초기상태 HKUST- 1과 동일하였다 (도 10 참조) .  The IR spectrum of HKUST-1 regenerated by external base addition was the same as the initial state HKUST-1 (see FIG. 10).

염기를 외부 첨가하는 것에 의한 재생 절차로서， 먼저 손상된 HKUST-1을 HC1 용액과 같은 강산 용액을 이용하여 용해시키고， 적정량의 NaOH 용액올 첨가하여 용액의 pH를 조절하였다. .  As a regeneration procedure by external addition of the base, the damaged HKUST-1 was first dissolved using a strong acid solution such as HC1 solution, and an appropriate amount of NaOH solution was added to adjust the pH of the solution. .

염기 첨가량이 손상된 HKUST-1의 용해에 사용된 산의 사용량보다 현저히 적더라도, HKUST-1을 재생할 수 있었다 (도 11 참조) . 산 1 당량에 대하여 0 .75 당량의 염기 첨가에 의해 재생된 HKUST— 1의 PXRD 패턴은 초기상태의 HKUST— 1와 동일하였고 (도 4a 참조)， 재생된 HKUST-1의 기공도도 역시 초기상태의 HKUST-1과 동일하였으나 (도 4b 참조)， HKUST-1의 회복률은 38%에 불과하였다. 한편, 동일 당량으로 염기를 첨가하였을 경우에는， 재생된 HKUST-1의 회복 수율이 87%의 매우 높은 수치에 달하였다.  Even if the amount of base addition was significantly less than the amount of acid used for dissolution of damaged HKUST-1, HKUST-1 could be regenerated (see FIG. 11). The PXRD pattern of HKUST-1 regenerated by adding 0.775 equivalents of base per equivalent of acid was the same as that of HKUST-1 in the initial state (see FIG. 4A), and the porosity of the regenerated HKUST-1 was also in the initial state. Was the same as HKUST-1 (see Figure 4b), but the recovery rate of HKUST-1 was only 38%. On the other hand, when the base was added in the same amount, the recovery yield of regenerated HKUST-1 reached a very high value of 87%.

다른 한편으로， 염기 첨가량이 산의 사용량보다 현저히 클 경우ᅳ HKUST- 1은 재생되기 어려웠다. 산 1 당량 대비 1 .25 당량의 수산화나트륨 첨가에 의해 얻어진 결정 생성물의 PXRD 패턴은 초기상태의 HKUST-1과는 달랐다. 결정 생성물의 질소 흡착 등은선으로부터 계산된 BET 비표면적은 270m2/g에 불과하였다. 외부 염기 첨가에 의해 재생된 HKUST-1 결정의 치수가 내부 염기 생성에 의해 재생된 HKUST— 1의 치수보다 훨씬 작음에도 불구하고, 이들 재생된 HKUST-1의 BET 비표면적은 모두 재생 절차와 관계없이 초기상태의 HKUST-1과 동일하였다. On the other hand, when the amount of base addition was significantly larger than the amount of acid used, HKUST-1 was difficult to regenerate. The PXRD pattern of the crystal product obtained by adding 1.25 equivalents of sodium hydroxide to 1 equivalent of acid was different from that of HKUST-1 in the initial state. The BET specific surface area calculated from the nitrogen adsorption line and the like of the crystal product was only 270 m 2 / g. Although the dimensions of HKUST-1 crystals regenerated by external base addition are much smaller than those of HKUST— regenerated by internal base generation, the BET specific surface area of these regenerated HKUST-1 are all independent of the regeneration procedure. Same as the initial HKUST-1.

M0F-5의 복원이 산의 종류에 영향을 받는 것과는 달리， HKUST-1은 손상된 Unlike the restoration of the M0F-5, which is affected by the type of acid, the HKUST-1

HKUST-1의 용해에 사용된 강산의 종류에 크게 영향을 받지 않고 재생될 수 있다. HKUST-1은 손상된 HKUST-1을 질산에 녹인 용액으로부터 재생될 수 있다 (도 12 내지 14 참조) . It can be regenerated without being greatly influenced by the type of strong acid used to dissolve HKUST-1. HKUST-1 can be regenerated from a solution in which damaged HKUST-1 is dissolved in nitric acid (see FIGS. 12-14).

이와 같은 외부 염기 첨가에 의한 재생은 매우 빠른 반웅이라는 점에서 의미가 있다. 종래의 HKUST-1의 재생 반응이 모두 1시간 동안 수행되었던 것과는 달리, 본 발명에 따른 반웅은 1분 내에 완료될 수 있다. 본 발명에 따라 1분 내에 재생한 HKUST— 1는， 회복 수율 뿐만 아니라 기공도 등의 다른 물성 면에서도 모두 종래의 1시간 동안 재생된 HKUST-1과 비교하여 거의 차이가 없다 (도 15 내지 18 참조) . 시험예 4: 서로다른손상샘플들의 흔합물로부터 재생된 HKUST-1의 분석 앞서의 실시예 4에서는 서로 다른 HKUST-1의 손상 샘플들의 흔합물을 외부 염기 첨가 방식을 통해 재생하였다.  Regeneration by the addition of such an external base is significant in that it is very fast reaction. Unlike all the regeneration reactions of the conventional HKUST-1 were performed for 1 hour, the reaction according to the present invention can be completed within 1 minute. The HKUST-1 regenerated within 1 minute according to the present invention has almost no difference in comparison with HKUST-1 regenerated for 1 hour in terms of recovery yield as well as other properties such as porosity (see FIGS. 15 to 18). ). Test Example 4 Analysis of HKUST-1 Regenerated from Mixtures of Different Damage Samples In Example 4 above, the mixture of damaged samples of different HKUST-1 was regenerated by an external base addition method.

그 결과 결정형의 HKUST-1을 약 92% 수율로 재생할 수 있었다 (도 19 참조) . 재생된 HKUST-1에 대해， IR 스펙트럼， PXRD 및 질소 흡착 시험을 통해， 초기상태의 HKUST-1와 비교하였다 (도 20 내지 22 참조) .  As a result, the crystalline HKUST-1 could be recovered in about 92% yield (see FIG. 19). The regenerated HKUST-1 was compared with the initial state of HKUST-1 through IR spectra, PXRD and nitrogen adsorption tests (see FIGS. 20 to 22).

재생된 HKUST-1의 PXRD 패턴 및 IR 스펙트럼은 초기상태의 HKUST-1와 동일하였고, 재생된 HKUST-1의 기공도도 초기상태의 HKUST-1에 비견할 만하였다.  The PXRD pattern and IR spectrum of the regenerated HKUST-1 were identical to those of the initial HKUST-1, and the porosity of the regenerated HKUST-1 was comparable to that of the initial HKUST-1.

Claims

【청구의 범위】 [Range of request] 【청구항 1】  [Claim 1] (1) 손상된 금속 -유기 골격체 (metal-organic framework ： MOF)를 산으로 처리하는 단계; 및  (1) treating the damaged metal-organic framework (MOF) with an acid; And (2) 상기 산 처리된 금속 -유기 골격체를 아미드 처리하거나 염기 처리하여 재생하는 단계를 포함하는, 금속 -유기 골격체의 재생방법.  (2) regenerating the acid-treated metal-organic skeleton by amide treatment or base treatment. 【청구항 2] [Claim 2] 제 1 항에 있어서，  The method of claim 1, 상기 금속 -유기 골격체가 M0F-5(IRM0F-1), HKUST-1 , IRMOF-2, IRM0F-3, IRMOF-4, IRMOF-5, IRMOF-6, IRMOF-7, IRMOF-8, IRM0F-9, I丽 OF-10, IRM0F-11, IRMOF-12, IRMOF-13, IRMOF-14, IRMOF-15, IRMOF-16, MOF— 74(Mg), M0F-74(Fe), MOF— 74(Co), MOF— 74(Ni), M0F-74(Zn) , MOF- 14, MOF— 177， MOF-508, UMCM-1, DUT-9, UiO-BPY, UiO-67, ZrMOF-BIPY, UiO-68, MOF-802, MOF-804, MOF-805, MOF-806 및 MOF-808로 이루어진 군으로부터 선택되는 적어도 하나를 포함하는 것을 특징으로 하는， 금속 -유기 골격체의 재생방법.  The metal-organic framework is M0F-5 (IRM0F-1), HKUST-1, IRMOF-2, IRM0F-3, IRMOF-4, IRMOF-5, IRMOF-6, IRMOF-7, IRMOF-8, IRM0F-9 , I 丽 OF-10, IRM0F-11, IRMOF-12, IRMOF-13, IRMOF-14, IRMOF-15, IRMOF-16, MOF— 74 (Mg), M0F-74 (Fe), MOF— 74 (Co ), MOF— 74 (Ni), M0F-74 (Zn), MOF-14, MOF— 177, MOF-508, UMCM-1, DUT-9, UiO-BPY, UiO-67, ZrMOF-BIPY, UiO- 68, MOF-802, MOF-804, MOF-805, MOF-806 and MOF-808, characterized in that it comprises at least one selected from the group consisting of. 【청구항 3] [Claim 3] 제 1 항에 있어서， . The method of claim 1, wherein . 상기 손상된 금속 -유기 골격체가 물 또는 증기에 의해 손상된 금속 -유기 골격체를 포함하는 것을 특징으로 하는， 금속 -유기 골격체의 재생방법.  And wherein said damaged metal-organic framework comprises a metal-organic framework damaged by water or steam. 【청구항 4】 [Claim 4] 제 1 항에 있어서，  The method of claim 1, 상기 산 처리가 상기 손상된 금속 -유기 골격체를 알콜， 물， 디메틸포름아미드， 아세톤， 사염화탄소， 클로로포름， 다이클로로메테인, 디메틸아세트아미드， 디에틸포름아미드, 디메틸설폭사이드， 벤젠， 를루엔， 또는 이들의 흔합 용매 중에서 교반시키는 것을 특징으로 하는， 금속ᅳ유기 골격체의 재생방법 The acid treatment is performed by treating the damaged metal-organic framework with alcohol, water, dimethylformamide, acetone, carbon tetrachloride, chloroform, dichloromethane, dimethylacetamide, diethylformamide, dimethylsulfoxide, benzene, toluene, or Of metal-organic skeletons, which is stirred in these mixed solvents. How to play 【청구항 5】 [Claim 5] 게 1 항에 있어서，  According to claim 1, 상기 아미드 처리가 상기 산 처리된 금속 -유기 골격체를 60 내지 15CTC의 온도 조건 하에 아미드계 용매 중에서 교반시키는 것을 포함하는 것을 특징으로 하는， 금속—유기 골격체의 재생방법.  Wherein said amide treatment comprises stirring said acid treated metal-organic framework in an amide solvent under a temperature condition of 60 to 15 CTC. 【청구항 6】 [Claim 6] 제 5 항에 있어서，  The method of claim 5, 상기 아미드 처리를 통해 자체적으로 내부에 염기가 생성 ( in s i tu - base generat ion)되는 것을 특징으로 하는, 금속 -유기 골격체의 재생방법.  A method of regenerating a metal-organic skeleton, characterized in that a base is generated in itself through the amide treatment. 【청구항 7] [Claim 7] 제 5 항에 있어서，  The method of claim 5, 상기 아미드 처리가 용매열 반웅 (solvothermal react ion)을 포함하는 것을 특징으로 하는， 금속 -유기 골격체의 재생방법 .  The method of regenerating a metal-organic skeleton, wherein the amide treatment comprises a solvothermal react ion. 【청구항 8】 [Claim 8] 제 5 항에 있어서，  The method of claim 5, 상기 아미드계 용매가 Ν ,Ν' -디에틸포름아미드， Ν ,Ν ' -디메틸포름아미드， 또는 이들의 흔합 용매를 포함하는 것을 특징으로 하는， 금속 -유기 골격체의 재생방법.  The method of regenerating a metal-organic skeleton, characterized in that the amide solvent comprises Ν, Ν'-diethylformamide, Ν, Ν'-dimethylformamide, or a mixed solvent thereof. 【청구항 9】 [Claim 9] 거 1 1 항에 있어서，  According to the clause 1 1, 상기 염기 처리가 상기 산 처리된 금속 -유기 골격체를 상온 조건 하에 염기성 용매 중에서 교반시키는 것을 포함하는 것을 특징으로 하는， 금속 -유기 골격체의 재생방법 Wherein the base treatment comprises stirring the acid treated metal-organic framework in a basic solvent under room temperature conditions, metal-organic Regeneration method of the skeleton 【청구항 10] [Claim 10] 제 9 항에 있어서,  The method of claim 9, 상기 염기성 용매가 상기 산 1 당량에 대해서 0.75 내지 1 당량의 양으로 사용되는 것을 특징으로 하는， 금속 -유기 골격체의 재생방법 .  The basic solvent is used in an amount of 0.75 to 1 equivalent based on 1 equivalent of the acid. 【청구항 11】 [Claim 11] 제 9 항에 있어서，  The method of claim 9, 상기 염기성 용매가 수산화나트륨 수용액, 수산화칼륨 수용액， 또는 이들의 흔합 용매를 포함하는 것을 특징으로 하는, 금속 -유기 골격체의 재생방법.  The basic solvent comprises an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, or a mixed solvent thereof. 【청구항 12] [Claim 12] 제 1 항에 있어서,  The method of claim 1, 상기 금속 -유기 골격체가 M0F-5 , HKUST-1 또는 이들의 흔합물을 포함하고, 상기 아미드 처리가 상기 산 처리된 금속 -유기 골격체를 60 내지 150°C의 온도 조건 하에 아미드계 용매 중에서 교반시키는 것을 포함하는 것을 특징으로 하는， 금속—유기 골격체의 재생방법 .  The metal-organic framework comprises M0F-5, HKUST-1 or a mixture thereof, and the amide treatment stirs the acid treated metal-organic framework in an amide solvent under a temperature condition of 60 to 150 ° C. A method of regenerating metal-organic frameworks, characterized by including 【청구항 13] [Claim 13] 제 1 항에 있어서，  The method of claim 1, 상기 금속—유기 골격체가 HKUST-1를 포함하고，  The metal—organic framework comprises HKUST-1, 상기 염기 처리가 상기 산 처리된 금속 -유기 골격체를 상온 조건 하에 염기성 용매 중에서 교반시키는 것을 포함하는 것을 특징으로 하는， 금속 -유기 골격체의 재생방법.  Wherein said base treatment comprises stirring said acid treated metal-organic framework in a basic solvent under room temperature conditions. 【청구항 14】 [Claim 14] 제 1 항에 있어서, 상기 단계 (2)를 거쳐 재생된 금속 -유기 골격체는， 손상되기 이전의 금속- 유기 골격체에 대비하여， 90% 이상의 기공도 및 BET 비표면적을 회복하는 것을 특징으로 하는， 금속 -유기 골격체의 재생방법 . The method of claim 1, The metal-organic skeleton, which has been regenerated through the step (2), recovers porosity and BET specific surface area of 90% or more as compared to the metal-organic framework before being damaged. How to Play Sieves. 【청구항 15] [Claim 15] 제 1 항에 있어서，  The method of claim 1, 상기 단계 (2)의 아미드 처리 또는 염기 처리가 상기 산 처리된 금속 -유기 골격체에 금속 이은을 더 첨가한 이후에 수행되는 것을 특징으로 하는， 금속 -유기 골격체의 재생방법.  The method of regenerating a metal-organic skeleton, characterized in that the amide treatment or base treatment of step (2) is performed after further addition of metal silver to the acid-treated metal-organic framework.
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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111111784B (en) * 2019-12-12 2022-09-13 广东省石油与精细化工研究院 UiO-67 coated Co catalyst and preparation method and application thereof
NZ793938A (en) 2020-03-31 2025-10-31 Numat Tech Inc Modified metal-organic framework (mof) compositions, process of making and process of use thereof
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Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
BLANCO-BRIEVA, G. ET AL.: "Thermal Regeneration of the Metal Organic Frameworks Used in the Adsorption of Refractory Organosulfur Compounds from Liquid Fuels", FUEL, vol. 105, 2013, pages 459 - 465, XP055348550 *
MAJANO, GERARDO ET AL.: "Solvent-mediated Reconstruction of the Metal-organic Framework HKUST-1 (Cu3(BTC)2", ADVANCED FUNCTIONAL MATERIALS, vol. 24, no. 25, 2014, pages 3855 - 3865, XP001590247 *
RAGANATI, F. ET AL.: "C02 Capture Performance of HKUST-1 in a Sound Assisted Fluidized Bed", CHEMICAL ENGINEERING JOURNAL, vol. 239, 2014, pages 75 - 86, XP055348634 *
SUN, XUEJIAO ET AL.: "A Novel Mechanochemical Method for Reconstructing the Moisture-degraded HKUST-1", CHEMICAL COMMUNICATIONS, vol. 51, no. 54, 2015, pages 10835 - 10838, XP055348547, [retrieved on 20150527] *
YE , SHENG ET AL.: "Post-combustion C02 Capture with the HKUST-1 and MIL-101(Cr) Metal-organic Frameworks: Adsorption, Separation and Regeneration Investigations", MICROPOROUS AND MESOPOROUS MATERIALS, vol. 179, 2013, pages 191 - 197, XP028689356 *

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