자원환경지질 (Economic and Environmental Geology)

  • 제52권6호
  • /
  • Pages.509-517
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  • 2019
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  • 1225-7281(pISSN)
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  • 2288-7962(eISSN)
대한자원환경지질학회 (The Korean Society of Economic and Environmental Geology)
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버네사이트 합성 시 합성 방법 및 양이온 조건에 따른 생성 광물 및 열수처리 후 상전이 특성

Mineral Products and Characteristics of Phase Transformation after Hydrothermal Treatment according to the Synthetic Method and Cation Combination during Birnessite Synthesis

  • 민소영 (경북대학교 지구시스템과학부) ;
  • 김영규 (경북대학교 지구시스템과학부)
  • Min, Soyoung (School of Earth System Sciences, Kyungpook National University) ;
  • Kim, Yeongkyoo (School of Earth System Sciences, Kyungpook National University)
  • 투고 : 2019.08.12
  • 심사 : 2019.11.28
  • 발행 : 2019.12.28
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초록

망간단괴를 주로 이루고 있는 망간산화물 버네사이트(7Å manganate, δ-MnO2)는 지표의 주요한 망간 광물로서 다양한 합성법이 연구되어 있으며 또한 토도로카이트 합성의 전구물질이기도 하다. 본 연구에서는 기존에 연구된 합성방법들 가운데 산화-환원반응을 합성기작으로 하는 Feng et al.(2004)와 Luo et al.(1998)의 방법, 환원반응을 합성기작으로 하는 Ma et al.(1999)의 방법 총 3 가지 방법을 참고하여 버네사이트 합성 조건 중 합성에 사용되는 염기(OH-)와 과망간산(MnO4-) 시약의 양이온 종류에 따른 합성 결과물의 특성을 연구하였다. 합성 시약의 양이온을 Na+와 K+ 두 이온으로 조합하여 총 12 가지 버네사이트를 합성하였다. 합성한 버네사이트의 구성 광물종은 XRD를 통해 동정하고 ICP를 통해 광물내의 두 이온 조성비를 측정하였다. 버네사이트를 전구물질로 한 부저라이트(buserite)를 열수처리한 생성물에 대한 XRD 분석 후 토도로카이트로의 상변이 유무 및 양상을 비교하였다. 그 결과 합성 방법마다 부산물 및 상전이 특성이 다른 경향성으로 나타났으며, 산화-환원반응기작 합성 방법에서 두 방법 모두 허스마나이트(hausmannite, γ-Mn3O4)와 페이크네타이트(feitknechtite, β-MnOOH)가 부산물로 생성되었다. Feng et al.(2004)의 방법에서는 망가나이트(manganite, γ-MnOOH) 상이 Na+가 지배적으로 존재하는 조건에서만 나타났다. 산화-환원반응 기작으로 합성한 두 가지 버네사이트는 공통적으로 NaOH, KMnO4를 사용하여 합성한 시료에서 토도로카이트(todorokite, 10Å manganate, OMS-1)로의 상전이가 나타났다. Ma et al.(1999)의 방법에서는 단일 상의 버네사이트가 합성되었고, 양이온을 Na+으로만 합성한 시료에서만 상전이를 확인하였다.

The birnessite (7Å manganate, δ-MnO2) which is a manganese oxide and comprises manganese nodules, is a major manganese mineral on the earth surface and a precursor in the synthesis of todorokite. In this study birnessite was synthesized by three different methods: Feng et al. (2004) and Luo et al. (1998) based on redox reaction and Ma et al. (1999) based on reduction reaction. 12 birnessite samples were synthesized by different combinations of Na+ and K+ cations based on the base (OH-) and permanganate (MnO4-) reagents in the synthesis. The mineral compositions of synthesized birnessite were identified by XRD, and the two cation ratio in the mineral was measured by ICP. The products obtained after hydrothermal treatment of Mg-buserite, by the precursor of birnessite, was examined by XRD, and then phase transition to todorokite and their characteristics were compared. Our results show that the byproducts and the characteristics of phase transition by each synthetic method have different trends. Hausmannite (γ-Mn3O4) and feitknechtite (β-MnOOH) were formed by both methods in the redox reaction mechanism. By Feng et al. (2004)'s method, manganite (γ-MnOOH) phase only appeared when cation was predominantly Na+. Two birnessite samples synthesized by redox reaction mechanism showed phase transition to todorokite (10Å manganate, OMS-1) when both NaOH and KMnO4 were used together. However, single-phase birnessite was formed by Ma et al. (1999)'s method, and phase transition was confirmed only for the sample when the cation was only composed of Na+.

키워드

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