KR20100093419A - Method of preparing layered double hydroxides by using metal hydroxides - Google Patents

Method of preparing layered double hydroxides by using metal hydroxides Download PDF

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KR20100093419A
KR20100093419A KR1020090012593A KR20090012593A KR20100093419A KR 20100093419 A KR20100093419 A KR 20100093419A KR 1020090012593 A KR1020090012593 A KR 1020090012593A KR 20090012593 A KR20090012593 A KR 20090012593A KR 20100093419 A KR20100093419 A KR 20100093419A
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hydroxide
iron
layered double
trivalent metal
metal salt
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KR101067900B1 (en
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박만
최충렬
김광섭
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경북대학교 산학협력단
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14Methods for preparing oxides or hydroxides in general
    • C01B13/18Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
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    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/02Oxides or hydroxides
    • CCHEMISTRY; METALLURGY
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    • C01G49/00Compounds of iron
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/03Particle morphology depicted by an image obtained by SEM

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Abstract

PURPOSE: The layered dihydroxide of the high purity can be manufactured with the process of being simplified. Since 2 can omit the solubilization and alkali material additive process of the metal salt, the process is simple and the manufacturing time can be reduced conspicuously. CONSTITUTION: The manufacturing method of the layered dihydroxide. For 2, 3 adds the solution of the metal salt in the suspension of the metal hydroxide. 3 a part of metal to metal the isomorphous substitution and 2 manufactures the layered dihydroxide(c). 2 is the metal hydroxide. It is selected from the group consisting of the calcium hydroxide, magnesium hydroxide, copper hydroxide, zi hydroxide, hydroxide nickel, manganese hyaroxide, the tin hydroxide and hydroxide molybdenum.

Description

금속수산화물을 이용한 층상이중수산화물의 제조방법{Method of preparing layered double hydroxides by using metal hydroxides}Method of preparing layered double hydroxides by using metal hydroxides

본 발명은 층상이중수산화물(Layered double hydroxides, LDHs)을 제조하는 방법에 관한 것으로, 더욱 상세하게는 2가 금속수산화물과 3가 금속염을 이용하여 고순도의 층상이중수산화물을 단순화된 공정으로 제조하는 새로운 방법에 관련된 것이다.The present invention relates to a method for preparing layered double hydroxides (LDHs), and more particularly to a novel method for preparing a highly purified layered double hydroxide using a divalent metal hydroxide and a trivalent metal salt in a simplified process. Related to.

층상이중수산화물은 수활석(brucite)의 구조와 비슷한 정팔면체의 금속 시트(sheet)로 구성된 판상형 점토광물로서 주로 2가 금속들이 크기가 비슷한 3가의 금속으로 부분적으로 동형치환되어 결정구조에 양하전을 띄는 점토광물이다. Layered double hydroxide is a plate-like clay mineral consisting of a sheet of octahedron, similar to the structure of a brucite, and is a clay that is positively charged in the crystal structure by partially isomorphic substitution of trivalent metals with similar sizes. It is a mineral.

층상이중수산화물의 구조식은 [M 1- x M x (OH)2] x +Az/n n-·mH2O (M, M = 2, 3가 금속 이온, A = 무기 및 유기 음이온, m = 층간 물분자 수, x = 하전밀도)로서 2, 3가의 금속이온과 무기-유기 음이온의 다양한 조합이 가능하다. Structural formula of the layered double hydroxide is [M II 1- x M III x (OH) 2 ] x + A z / n n - m H 2 O (M II , M III = 2, trivalent metal ion, A = inorganic And organic anions, m = number of interlayer water molecules, x = charge density), various combinations of divalent, trivalent metal ions and inorganic-organic anions are possible.

따라서 이러한 층상이중수산화물의 높은 음이온 교환능력, 층간팽창능력, 산분해성 및 탄산이온 친화력 등과 같은 독특한 성질을 이용하여 촉매제, 이온교환 제, 흡착제, 세라믹 전구체, 약품 전달체, 전극, 필름, 광학기억소자, 분리제 및 유-무기 나노혼합물 합성 등의 광범위한 분야에서 활용되고 있다. Therefore, the catalyst, ion exchanger, adsorbent, ceramic precursor, drug carrier, electrode, film, optical memory device, using the unique properties such as high anion exchange capacity, interlaminar expansion capacity, acid decomposability and carbonate affinity of the layered double hydroxide It is used in a wide range of fields such as separation agent and organic-inorganic nanomixture synthesis.

지금까지 이러한 층상이중수산화물을 제조하는 가장 간단하면서도 일반적으로 사용하는 방법으로는 공침법이 있다. 이 방법은 염소, 질산 및 초산 이온을 함유한 2가 금속(Ca, Mg, Cu, Zn, Ni, Co 등)과 3가 금속(Al, Fe, Cr 등)을 완전히 용해한 후 알칼리 물질(NaOH, KOH, NH4OH 등)을 첨가하여 공침시키고, 결정성 및 생산성을 높이기 위하여 수시간∼수일 동안 열처리하여 층상이중수산화물을 제조하는 방법인데, 공정이 복잡하고 시간이 오래 소요되는 문제점이 있다. To date, the simplest and most commonly used method of preparing such layered double hydroxides is the coprecipitation method. This method completely dissolves divalent metals (Ca, Mg, Cu, Zn, Ni, Co, etc.) and trivalent metals (Al, Fe, Cr, etc.) containing chlorine, nitric acid, and acetate ions, followed by alkali (NaOH, KOH, NH 4 OH, etc.) is co-precipitated and heat-treated for several hours to several days in order to increase crystallinity and productivity, a method for producing a layered double hydroxide, there is a problem that the process is complicated and takes a long time.

더욱이 금속산화물 및 금속수산화물을 이용하여 층상이중수산화물을 제조하는 종래의 방법은 이들 금속의 용해도가 매우 낮기 때문에 용해 및 재결정화 되는데 수주~수개월 소요되므로 보다 효과적인 제조방법의 개발이 요구된다. Furthermore, the conventional method for producing layered double hydroxides using metal oxides and metal hydroxides requires several weeks to several months to dissolve and recrystallize because of the low solubility of these metals.

본 발명은 상술한 종래의 층상이중수산화물을 제조하는 방법에 있어서의 문제점을 개선하여, 간단한 공정을 통해 단시간 내에 층상이중수산화물을 얻을 수 있는 효율적인 방법을 제공하는 것을 목적으로 한다.It is an object of the present invention to improve the problems in the conventional method for producing a layered double hydroxide described above, and to provide an efficient method for obtaining a layered double hydroxide in a short time through a simple process.

본 발명에 따른 금속수산화물을 이용한 층상이중수산화물의 제조방법은,Method for producing a layered double hydroxide using a metal hydroxide according to the present invention,

2가 금속수산화물 현탁액에 3가 금속염의 용액을 첨가하여 2가 금속의 일부를 3가 금속으로 동형치환하여 층상이중수산화물을 제조하는 것을 기본적인 구성으로 한다. The basic structure is to prepare a layered double hydroxide by adding a solution of a trivalent metal salt to a divalent metal hydroxide suspension and isotopically replacing a part of the divalent metal with a trivalent metal.

본 발명의 방법에 따르면, 2가 금속수산화물 현탁액에 3가 금속염의 용액을 첨가하면, 2가 금속수산화물의 결정형태가 그대로 유지되는 가운데 2가 금속의 일부가 3가 금속으로 동형치환하여 층분리 현상에 의해 층상이중수산화물이 제조된다. According to the method of the present invention, when a solution of a trivalent metal salt is added to a divalent metal hydroxide suspension, the crystalline form of the divalent metal hydroxide remains intact, and a part of the divalent metal is homogeneously substituted with the trivalent metal, resulting in layer separation. The layered double hydroxide is prepared by.

본 발명의 방법에 따라 층상이중수산화물을 제조할 경우, 고순도의 층상이중수산화물을 단순화된 공정으로 제조할 수 있는 효과가 있다.When the layered double hydroxide is prepared according to the method of the present invention, there is an effect that a high purity layered double hydroxide can be prepared by a simplified process.

특히, 종래의 층상이중수산화물의 제조공정에 있어서의 2가 금속염의 가용화 및 알칼리 물질 첨가 과정을 생략할 수 있으므로 공정이 간단하여 제조시간을 획기적으로 단축할 뿐만 아니라, 보다 고순도의 층상이중수산화물을 제조할 수 있다.In particular, since the solubilization of the divalent metal salt and the addition of alkali substance in the conventional manufacturing process of the layered double hydroxide can be omitted, the process is simple and the manufacturing time can be drastically shortened, and a higher purity layered double hydroxide is produced. can do.

본 발명에 따르면, 2가 금속수산화물 현탁액에 3가 금속염의 용액을 첨가하여 2가 금속의 일부를 3가 금속으로 동형치환하여 층상이중수산화물을 제조하는 방법이 제공된다.According to the present invention, there is provided a method for producing a layered double hydroxide by adding a solution of a trivalent metal salt to a divalent metal hydroxide suspension to homomorphize a portion of the divalent metal into a trivalent metal.

본 발명의 방법에 따르면, 2가 금속수산화물의 현탁액을 만들어 3가 금속염을 용해시킨 용액을 서서히 첨가하면, 2가 금속 수산화물의 결정에서 2가 금속이온이 3가 금속이온으로 동형치환되어 양하전이 생성되고, 이 양하전을 중화하기 위하여 3가 금속염을 구성하는 음이온이 결정의 층간으로 유입되어, 2가 금속의 일부가 3가 금속으로 치환된 금속수산화물 결정의 층간 분리(delamination) 현상이 일어나 얇은 판상의 층상이중수산화물이 형성된다.According to the method of the present invention, when a suspension of divalent metal hydroxide is made and a solution of the trivalent metal salt is slowly added, the divalent metal ion is homogenously substituted into the trivalent metal ion in the crystal of the divalent metal hydroxide to generate positive charge. In order to neutralize this positive charge, anions constituting the trivalent metal salt flow into the interlayers of the crystals, and a delamination phenomenon of the metal hydroxide crystals in which a part of the divalent metals are replaced with the trivalent metals occurs, resulting in a thin plate shape. Layered double hydroxides are formed.

여기서, 상기 2가 금속수산화물로는 수산화칼슘[Ca(OH)2], 수산화마그네슘[Mg(OH)2], 수산화구리[Cu(OH)2], 수산화아연[Zn(OH)2], 수산화니켈[Ni(OH)2], 수산화망간[Mn(OH)2], 수산화주석[Sn(OH)2] 및 수산화몰리브덴[Mo(OH)2]으로 이루어진 군에서 선택되는 것을 들 수 있으며, 상기 3가 금속염은 바람직하게는 철(Fe), 알루미늄(Al), 및 크롬(Cr)의 산성염, 예컨대 이들 3가 금속의 염소, 질산, 초산염 등이 사용될 수 있다. 이러한 3가 금속염으로서는 염화철(FeCl3), 염화알루미늄(AlCl3), 염화크롬(CrCl3), 질산철[Fe(NO3)3], 질산알루미늄[Al(NO3)3], 질산크롬[Cr(NO3)3], 황산철[Fe2(SO4)3], 황산알루미늄[Al2(SO4)3], 황산크롬[Cr2(SO4)3], 초 산철[Fe(CH3COO)3], 초산알루미늄[Al(CH3COO)3], 초산크롬[Cr(CH3COO)3], 과염소산철[Fe(ClO4)3], 플루오르화철[FeCl3], 브롬화철[FeBr3], 구연산철[FeC6H5O7] 및 옥살산철[Fe2(C2O4)3]로 이루어진 군에서 선택되는 것을 들 수 있다. 상기 2가 금속수산화물과 3가 금속염은 어느 한 종류 단독으로 사용될 수도 있고, 혼합하여 사용할 수도 있다.Here, as the divalent metal hydroxide, calcium hydroxide [Ca (OH) 2 ], magnesium hydroxide [Mg (OH) 2 ], copper hydroxide [Cu (OH) 2 ], zinc hydroxide [Zn (OH) 2 ], nickel hydroxide [Ni (OH) 2 ], manganese hydroxide [Mn (OH) 2 ], tin hydroxide [Sn (OH) 2 ], and molybdenum hydroxide [Mo (OH) 2 ]. The metal salt is preferably an acid salt of iron (Fe), aluminum (Al), and chromium (Cr), such as chlorine, nitric acid, acetate, etc. of these trivalent metals. Such trivalent metal salts include iron chloride (FeCl 3 ), aluminum chloride (AlCl 3 ), chromium chloride (CrCl 3 ), iron nitrate [Fe (NO 3 ) 3 ], aluminum nitrate [Al (NO 3 ) 3 ], and chromium nitrate [ Cr (NO 3 ) 3 ], iron sulfate [Fe 2 (SO 4 ) 3 ], aluminum sulfate [Al 2 (SO 4 ) 3 ], chromium sulfate [Cr 2 (SO 4 ) 3 ], iron acetate [Fe (CH 3 COO) 3 ], aluminum acetate [Al (CH 3 COO) 3 ], chromium acetate [Cr (CH 3 COO) 3 ], iron perchlorate [Fe (ClO 4 ) 3 ], iron fluoride [FeCl 3 ], iron bromide And those selected from the group consisting of [FeBr 3 ], iron citrate [FeC 6 H 5 O 7 ], and iron oxalate [Fe 2 (C 2 O 4 ) 3 ]. The divalent metal hydroxide and the trivalent metal salt may be used alone or in combination.

상기 2가 금속수산화물과 3가 금속염은 몰비로 1:1 내지 10:1이 되도록 하며, 상기 2가 금속수산화물의 현탁액에 3가 금속염을 서서히 첨가하여 알칼리성 조건하에서 주로 상온 근처에서 서서히 반응이 이루어지도록 한다. The divalent metal hydroxide and the trivalent metal salt may be 1: 1 to 10: 1 in a molar ratio, and the trivalent metal salt is gradually added to the suspension of the divalent metal hydroxide so that the reaction is performed slowly at about room temperature under alkaline conditions. do.

2가 금속수산화물과 3가 금속염의 가장 바람직한 몰비는 2∼4:1이며, 상기 범위 이상에서는 완전한 치환이 이루어지지 않아 2가 금속수산화물의 구조가 그대로 남아 있게 되어 층상이중수산화물의 수율이 낮아지며, 3가 금속염을 과량으로 투입하면 3가 금속의 침전이 발생할 수 있다. The most preferable molar ratio of the divalent metal hydroxide and the trivalent metal salt is 2 to 4: 1, and the substitution of the divalent metal hydroxide is not carried out so that the structure of the divalent metal hydroxide remains intact, resulting in a low yield of layered double hydroxide. Excessive addition of valent metal salts can result in precipitation of trivalent metals.

한편, 상기 2가 금속수산화물에 따라 가장 적정한 반응온도와 반응시간은 조금씩 달라질 수 있다. 즉, 2가의 수산화칼슘[Ca(OH)2]과 3가의 Fe 또는 Al 금속염을 사용할 경우, 혼합 후 상온에서 1시간 반응하였을 때 층상이중수산화물의 품질이 가장 우수하다. 반면에 2가의 수산화마그네슘[Mg(OH)2]과 3가 금속염을 사용할 경우에는 60℃ 에서 4시간 반응하는 것이 가장 적당하며, 상기 범위에서 벗어나면 다소의 불순물이 함께 생성되거나 순도가 낮아진다.Meanwhile, the most suitable reaction temperature and reaction time may vary slightly depending on the divalent metal hydroxide. That is, when bivalent calcium hydroxide [Ca (OH) 2 ] and trivalent Fe or Al metal salts are used, the quality of the layered double hydroxide is the best when reacted at room temperature for 1 hour after mixing. On the other hand, when using divalent magnesium hydroxide [Mg (OH) 2 ] and trivalent metal salt, it is most suitable to react at 60 ° C. for 4 hours, and if out of the above range, some impurities are produced together or the purity is lowered.

반응이 완료되면 반응생성물을 증류수로 수회 세척한 다음 건조한다. 건조는 70℃의 온도 근처에서 20시간 정도 실시한다.After the reaction is completed, the reaction product is washed several times with distilled water and then dried. Drying is performed for about 20 hours near the temperature of 70 degreeC.

이하, 실시예를 통해 본 발명을 좀 더 상세하게 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.

[실시예][Example]

실시예 1Example 1

0.2M Ca(OH)2(Junsei Chemical Co.) 현탁액 50 ml를 3개 준비하여, 여기에 0.1M FeCl3(Sigma Chemical Co.) 용액을 Ca(OH)2:FeCl3의 몰비가 각각 10:1, 5:1 및 2:1이 되도록 천천히 적가하고, 30 분간 교반하여 CaFe-층상이중수산화물을 제조하였다. 반응이 완료된 후, 반응생성물을 증류수로 수회 세척하고, 70℃의 온도에서 20시간 건조하였다.Three 50 ml suspensions of 0.2 M Ca (OH) 2 (Junsei Chemical Co.) were prepared, and a 0.1 M FeCl 3 (Sigma Chemical Co.) solution was added with a molar ratio of Ca (OH) 2 : FeCl 3 to 10: Slowly added dropwise to 1, 5: 1 and 2: 1, and stirred for 30 minutes to prepare a CaFe-layered double hydroxide. After the reaction was completed, the reaction product was washed several times with distilled water, and dried for 20 hours at a temperature of 70 ℃.

제조한 반응생성물을 X-선 회절분석하여, 결과를 도 1에 그래프로 나타내었다. 도 1에서 보는 것과 같이, FeCl3의 첨가 비율이 증가함에 따라 Ca(OH)2 피크는 점진적으로 사라지고 CaFe-층상이중수산화물 피크가 나타났으며, 몰비 2:1에서는 거의 대부분 CaFe-층상이중수산화물 피크만 나타나는 것을 확인할 수 있었다.The prepared reaction product was analyzed by X-ray diffraction, and the results are shown graphically in FIG. 1. As shown in FIG. 1, as the addition ratio of FeCl 3 increases, the Ca (OH) 2 peak gradually disappears, and a CaFe-layered dihydroxide peak appears, and at a molar ratio of 2: 1, the CaFe-layered double hydroxide peak is almost always. I could see that only appeared.

실시예 2Example 2

0.2M 농도의 Ca(OH)2 현탁액 50 ml를 준비하고, 여기에 0.1M FeCl3 용액 50 ml를 서서히 첨가하면서 pH 변화를 관찰하여, 그 결과를 도 2의 그래프로 나타내었다. 50 ml of a 0.2 M Ca (OH) 2 suspension was prepared, and pH change was observed while slowly adding 50 ml of 0.1 M FeCl 3 solution, and the results are shown in the graph of FIG. 2.

최초 0.2M Ca(OH)2 현탁액의 pH는 12.6으로 알칼리성이었으며, 0.1M FeCl3 용액의 첨가에 따라 점진적으로 낮아져, 0.1M FeCl3 30 ml가 첨가된 40분 후에는 pH가 급격히 감소되어 0.1M FeCl3 50 ml가 첨가된 60분에는 pH가 10.4로 감소하였다. 그러나, 반응이 진행되면서 120분 후에는 pH가 다시 11.3으로 올라가 평형을 유지하였다. The pH of the first 0.2 M Ca (OH) 2 suspension was alkaline at 12.6 and gradually decreased with the addition of 0.1 M FeCl 3 solution, resulting in a sharp decrease in pH 40 min after 30 ml of 0.1 M FeCl 3 was added to 0.1 M At 60 minutes with 50 ml of FeCl 3 , the pH was reduced to 10.4. However, after 120 minutes as the reaction proceeds, the pH rises to 11.3 to maintain equilibrium.

층상이중수산화물의 최적반응 pH가 10.0∼12.0인 것을 감안할 때, 상기 결과로부터 별도의 알칼리 물질을 첨가하지 않아도 최적의 pH를 유지하므로 층상이중수산화물을 단순한 공정으로 제조할 수 있음을 확인할 수 있었다.Considering that the optimum reaction pH of the layered double hydroxide is 10.0 to 12.0, it can be seen from the above result that the layered double hydroxide can be prepared by a simple process because the optimum pH is maintained without adding an alkaline substance.

실시예 3Example 3

0.2M Ca(OH)2(Junsei Chemical Co.) 현탁액을 5개 준비하여, 여기에 0.1M FeCl3(Sigma Chemical Co.) 용액을 Ca(OH)2:FeCl3의 몰비가 각각 10:1, 8:1, 6:1, 4:1 및 2:1이 되도록 천천히 적가하고, 30 분간 교반하여 CaFe-층상이중수산화물을 제조하였다. 반응이 완료된 후, 반응생성물을 증류수로 수회 세척하고, 70℃의 온도에서 20시간 건조하였다.Five 0.2 M Ca (OH) 2 (Junsei Chemical Co.) suspensions were prepared, and a 0.1 M FeCl 3 (Sigma Chemical Co.) solution was added with a molar ratio of Ca (OH) 2 : FeCl 3 of 10: 1, It was slowly added dropwise to 8: 1, 6: 1, 4: 1 and 2: 1, and stirred for 30 minutes to prepare CaFe-layered double hydroxide. After the reaction was completed, the reaction product was washed several times with distilled water, and dried for 20 hours at a temperature of 70 ℃.

이렇게 하여 생성된 CaFe-층상이중수산화물과 반응전의 수산화칼슘의 결정형태를 전자현미경으로 관찰하여, Ca(OH)2/FeCl3 몰 비율에 따른 결과를 도 3a 내지 도 3f에 나타내었다.The crystal form of CaFe-layered double hydroxide thus formed and calcium hydroxide before the reaction was observed under an electron microscope, and the results according to the Ca (OH) 2 / FeCl 3 molar ratio are shown in FIGS. 3A to 3F.

도 3a 내지 도 3f에서 보는 것과 같이, FeCl3 첨가비율이 증가할수록 Ca(OH)2의 두꺼운 층상이 얇은 판상의 층상이중수산화물로 변화되어, Ca(OH)2/FeCl3 몰 비율이 8∼10:1에서는 두꺼운 Ca(OH)2의 층상이 그대로 남아 있으나, 2∼4:1에서는 얇은 판상의 층상이중수산화물이 관찰되었다.As shown in FIGS. 3A to 3F, as the addition ratio of FeCl 3 increases, the thick layer of Ca (OH) 2 is changed into a thin plate-like layered double hydroxide, and the Ca (OH) 2 / FeCl 3 molar ratio is 8 to 10. In 1: 1, a thick layer of Ca (OH) 2 remained, but in 2-4: 1, a thin plate-like layered double hydroxide was observed.

실시예 4Example 4

0.2M Ca(OH)2(Junsei Chemical Co.) 현탁액을 준비하여, 여기에 0.1M Al(NO3)3(Sigma Chemical Co.) 용액을 천천히 적가하고, 30 분간 교반하여 CaAl-층상이중수산화물을 제조하였다. 반응이 완료된 후, 반응생성물을 증류수로 수회 세척하고, 70℃의 온도에서 20시간 건조하였다.A 0.2 M Ca (OH) 2 (Junsei Chemical Co.) suspension was prepared, and 0.1 M Al (NO 3 ) 3 (Sigma Chemical Co.) solution was slowly added dropwise and stirred for 30 minutes to remove CaAl-layered double hydroxide. Prepared. After the reaction was completed, the reaction product was washed several times with distilled water, and dried for 20 hours at a temperature of 70 ℃.

제조된 CaAl-층상이중수산화물과 반응전의 Ca(OH)2에 대해 적외선분광분석을 실시하여 얻어진 적외선분광분석 spectra를 도 4에 나타내었다. Infrared spectroscopy spectra obtained by performing an infrared spectroscopic analysis on the prepared CaAl-layered double hydroxide and Ca (OH) 2 before the reaction are shown in FIG. 4.

도면에서 보는 것과 같이, Ca(OH)2에 존재하지 않는 NO3 - 흡수 band가 CaAl-층상이중수산화물에서 명확하게 관찰되었다. CaAl-층상이중수산화물은 1020, 1350 및 2380 cm-1에서 NO3 -에 기인된 흡수 밴드가 관찰되었으며, 1600 cm-1 부근에서는 물 분자에 의한 흡수 밴드가 나타났다. 이와 같은 결과로부터 NO3-가 CaAl-층상이중수산화물 층간에 보상이온으로 존재하는 것을 확인할 수 있다.As shown in the figure, the NO 3 absorption band not present in Ca (OH) 2 was clearly observed in the CaAl-layered double hydroxide. The CaAl-layered double hydroxide showed absorption bands due to NO 3 at 1020, 1350, and 2380 cm −1 , and absorption bands by water molecules near 1600 cm −1 . From these results, it can be seen that NO 3- is present as a compensation ion between the CaAl-layered double hydroxide layers.

이러한 결과를 통해, Al(NO3)3의 첨가에 의해 Ca(OH)2의 Ca2+ 이온이 Al3+ 이 온으로 동형치환되어 양하전이 생성되고, 이 양하전을 NO3 - 이온이 중화하기 위하여 층간으로 유입되어, Ca(OH)2 층의 분리(delamination)가 일어났음을 확인할 수 있다. Through this result, Ca 2+ ions of Ca (OH) 2 are homozygous to Al 3+ ions by addition of Al (NO 3 ) 3 to generate positive charges, and NO 3 ions are neutralized. In order to enter the interlayer, it can be confirmed that delamination of Ca (OH) 2 layer occurred.

도 1은 실시예 1에서 제조한 반응생성물의 Ca(OH)2/FeCl3 몰 비율에 따른 X-선 회절분석(XRD) 패턴.1 is an X-ray diffraction analysis (XRD) pattern according to the Ca (OH) 2 / FeCl 3 molar ratio of the reaction product prepared in Example 1.

도 2는 실시예 2에서 0.2M Ca(OH)2 현탁액에 FeCl3 용액의 첨가에 따른 반응액의 pH 변화를 도시한 그래프.Figure 2 is a graph showing the pH change of the reaction solution according to the addition of FeCl 3 solution to 0.2M Ca (OH) 2 suspension in Example 2.

도 3a 내지 도 3f는 수산화칼슘과 실시예 3에서 제조된 CaFe-층상이중수산화물의 주사전자현미경사진으로, 순서대로 수산화칼슘과 Ca(OH)2/FeCl3 몰비 10:1, 8:1, 6:1, 4:1 및 2:1일 때의 결과.3A to 3F are scanning electron micrographs of calcium hydroxide and CaFe-layered double hydroxide prepared in Example 3, in which the molar ratio of calcium hydroxide and Ca (OH) 2 / FeCl 3 is 10: 1, 8: 1, 6: 1 , 4: 1 and 2: 1.

도 4는 실시예 4에서 제조된 Ca(OH)2 및 CaAl-층상이중수산화물의 적외선분광분석(FT-IR) 스펙트라.4 is an infrared spectroscopy (FT-IR) spectra of Ca (OH) 2 and CaAl-layered dihydroxide prepared in Example 4. FIG.

Claims (5)

2가 금속수산화물의 현탁액에 3가 금속염의 용액을 첨가하여 2가 금속의 일부를 3가 금속으로 동형치환하여 층상이중수산화물을 제조하는 것을 특징으로 하는 층상이중수산화물의 제조방법.A method for producing a layered double hydroxide, comprising adding a solution of a trivalent metal salt to a suspension of a divalent metal hydroxide to homogeneously replace a portion of the divalent metal with a trivalent metal to produce a layered double hydroxide. 제 1항에 있어서, 상기 2가 금속수산화물은 수산화칼슘[Ca(OH)2], 수산화마그네슘[Mg(OH)2], 수산화구리[Cu(OH)2], 수산화아연[Zn(OH)2], 수산화니켈[Ni(OH)2], 수산화망간[Mn(OH)2], 수산화주석[Sn(OH)2] 및 수산화몰리브덴[Mo(OH)2]으로 이루어진 군에서 선택되는 것을 특징으로 하는 층상이중수산화물 제조방법.The method of claim 1, wherein the divalent metal hydroxide is calcium hydroxide [Ca (OH) 2 ], magnesium hydroxide [Mg (OH) 2 ], copper hydroxide [Cu (OH) 2 ], zinc hydroxide [Zn (OH) 2 ] And nickel hydroxide [Ni (OH) 2 ], manganese hydroxide [Mn (OH) 2 ], tin hydroxide [Sn (OH) 2 ] and molybdenum hydroxide [Mo (OH) 2 ] Method for preparing layered double hydroxide. 제 1항에 있어서, 상기 3가 금속염은 3가 금속은 철, 알루미늄 및 크롬 중에서 선택되는 것을 특징으로 하는 층상이중수산화물의 제조방법.The method of claim 1, wherein the trivalent metal salt is a trivalent metal is selected from iron, aluminum and chromium. 제 3항에 있어서, 상기 3가 금속염은 염화철(FeCl3), 염화알루미늄(AlCl3), 염화크롬(CrCl3), 질산철[Fe(NO3)3], 질산알루미늄[Al(NO3)3], 질산크롬[Cr(NO3)3], 황산철[Fe2(SO4)3], 황산알루미늄[Al2(SO4)3], 황산크롬[Cr2(SO4)3], 초산철[Fe(CH3COO)3], 초산알루미늄[Al(CH3COO)3], 초산크롬[Cr(CH3COO)3], 과염소산 철[Fe(ClO4)3], 플루오르화철[FeCl3], 브롬화철[FeBr3], 구연산철[FeC6H5O7] 및 옥살산철[Fe2(C2O4)3]로 이루어진 군에서 선택되는 것을 특징으로 하는 층상이중수산화물의 제조방법.The method of claim 3, wherein the trivalent metal salt is iron chloride (FeCl 3 ), aluminum chloride (AlCl 3 ), chromium chloride (CrCl 3 ), iron nitrate [Fe (NO 3 ) 3 ], aluminum nitrate [Al (NO 3 ) 3 ], chromium nitrate [Cr (NO 3 ) 3 ], iron sulfate [Fe 2 (SO 4 ) 3 ], aluminum sulfate [Al 2 (SO 4 ) 3 ], chromium sulfate [Cr 2 (SO 4 ) 3 ], Iron acetate [Fe (CH 3 COO) 3 ], Aluminum acetate [Al (CH 3 COO) 3 ], Chromium acetate [Cr (CH 3 COO) 3 ], Iron perchlorate [Fe (ClO 4 ) 3 ], Iron fluoride [ Preparation of layered double hydroxide, characterized in that selected from the group consisting of FeCl 3 ], iron bromide [FeBr 3 ], iron citrate [FeC 6 H 5 O 7 ] and iron oxalate [Fe 2 (C 2 O 4 ) 3 ] Way. 제 1항에 있어서, 상기 2가 금속수산화물에 대한 3가 금속염의 몰비가 1:1 내지 10:1이 되도록 3가 금속염을 첨가하는 것을 특징으로 하는 층상이중수산화물의 제조방법. The method of claim 1, wherein a trivalent metal salt is added so that the molar ratio of the trivalent metal salt to the divalent metal hydroxide is 1: 1 to 10: 1.
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KR20210009828A (en) * 2019-07-18 2021-01-27 한국과학기술연구원 Composite of rice husk biochar and Layered double hydroxides and method for fabricating the same

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