Korean Journal of Mineralogy and Petrology (광물과 암석)

The Petrological Society of Korea & The Mineralogical Society of Korea (한국암석학회 & 한국광물학회)
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Characterization of Synthesized Carbonate and Sulfate Green Rusts: Formation Mechanisms and Physicochemical Properties

합성된 탄산염 및 황산염 그린 러스트의 형성 메커니즘과 이화학적 특성 규명

  • Lee, Seon Yong (Department of Earth and Environmental Sciences, Korea University) ;
  • Choi, Su-Yeon (Department of Earth and Environmental Sciences, Korea University) ;
  • Chang, Bongsu (Department of Earth and Environmental Sciences, Korea University) ;
  • Lee, Young Jae (Department of Earth and Environmental Sciences, Korea University)
  • 이선용 (고려대학교 지구환경과학과) ;
  • 최수연 (고려대학교 지구환경과학과) ;
  • 장봉수 (고려대학교 지구환경과학과) ;
  • 이영재 (고려대학교 지구환경과학과)
  • Received : 2022.06.13
  • Accepted : 2022.06.22
  • Published : 2022.06.30
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Abstract

Carbonate green rust (CGR) and sulfate green rust (SGR) commonly occur in nature. In this study, CGR and SGR were synthesized through co-precipitation, and their formation mechanisms and physicochemical properties were investigated. X-ray diffraction (XRD) and Rietveld refinement showed both CGR and SGR with layered double hydroxide structure were successfully synthesized without any secondary phases under each synthetic condition. Refined structural parameters (unit cell) for two green rusts were a (=b) = 3.17 Å and c = 22.52 Å for CGR and a (=b) = 5.50 Å and c = 10.97 Å for SGR with the crystallite size 57.8 nm in diameter from (003) reflection and 40.1 nm from (001) reflections, respectively. Scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) results showed that both CGR and SGR had typical hexagonal plate-like crystal morphologies but their chemical composition is different in the content of C and S. In addition, Fourier transform infrared (FT-IR) spectroscopy analysis revealed that carbonate (CO32-) and sulfate (SO42-) molecules were occupied as interlayer anions of CGR and SGR, respectively. These SEM/EDS and FT-IR results were in good agreement with XRD results. Changes in the solution chemistry (i.e., pH, Eh and residual iron concentrations (Fe(II):Fe(III)) of the mixed solution) were observed as a function of the injection time of hydroxyl ion (OH-) into the iron solution. Three different stages were observed in the formation of both CGR and SGR; precursor, intermediator, and green rust in the formation of both CGR and SGR. This study provides co-precipitation methods for CGR and SGR in a way of the stable synthesis. In addition, our findings for the formation mechanisms of the two green rusts and their physicochemical properties will provide crucial information with researches and industrials in utilizing green rust.

본 연구는 자연계에서 가장 흔하게 관찰되는 두 그린 러스트(green rust) 광물인 carbonate green rust (CGR)과 sulfate green rust (SGR)을 공침법(co-precipitation)을 통해 각각 합성하고, 이들의 형성 메커니즘 및 이화학적 특성들을 체계적으로 규명하였다. X-선 회절(XRD) 분석 및 리트벨트 정련 수행 결과, 본 합성 조건에서 이차광물상 없이 이중층수산화물로서 CGR과 SGR이 합성됨을 확인하였다. 또한, 각각의 구조 파라미터는 CGR의 경우 a(=b)축 = 3.17 Å, c축 = 22.52 Å이고, SGR의 경우 a(=b)축 = 5.50 Å, c축 = 10.97 Å이며, 이들의 미결정 크기는 각각 (003)면 기준 57.8 nm와 (001)면 기준 40.1 nm로 밝혀졌다. 주사전자현미경/에너지 분산형 분광분석(SEM/EDS) 결과, CGR과 SGR은 모두 육각 판상의 전형적인 이중층수산화물 결정 형상을 보이지만 탄소(C)와 황(S)의 함량은 서로 다르게 나타났다. 퓨리에 변환 적외선(FT-IR) 분광 분석결과, 탄산염(CO32-)와 황산염(SO42-) 이온들이 각각 CGR과 SGR의 층간 음이온으로 밝혀졌고, 이는 XRD를 활용한 광물상 동정 결과와 잘 일치한다. 철 용액으로의 수산화이온(OH-) 주입 시간에 따른 혼합 용액의 pH와 Eh, 그리고 잔류 철 농도의 비율(Fe(II):Fe(III)) 측정 결과, 시간에 따른 차이는 있지만 두 green rusts 모두 1단계 전구체 형성, 2단계 중간 생성물로의 상변환, 그리고 3단계 green rust로의 상변환과 에이징에 의한 결정성장으로 이어지는 결정 형성 메커니즘을 보이는 것으로 판단된다. 본 연구는 공침법을 통해 CGR과 SGR을 안정적으로 합성하고 이들의 형성 메커니즘과 이화학적 특성을 규명함으로써, green rust를 활용한 응용 연구 및 산업 활용에 원천 기초자료를 제공할 것으로 기대된다.

Keywords

Acknowledgement

이 논문은 정부의 재원으로 한국연구재단의 지원을 받아 수행된 연구임(No. 2020R1I1A1A01073846 and No. 2021R1A2C100601111). 또한, 고려대학교에서 지원된 연구비로 수행되었음. 모든 저자들은 본 논문의 최종본 제출에 동의하였음.

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