綠鏽 (化合物)

綠鏽（英語：Green rust）是一類含鐵(II)、鐵(III)混合價態氫氧化物的綠色晶體的總稱。這類晶體中，除了Fe²⁺、Fe³⁺和OH⁻外，還有可能有CO2−
3、Cl−
或SO2−
4等陰離子在其層狀雙氫氧化合物結構中，研究最多的物種有：^[1]

綠鏽碳酸鹽 - GR(CO2−
3)：[Fe2+
4Fe3+
2(HO−
)₁₂]²⁺ · [CO2−
3·2H
2O]²⁻.^[2]^[3]^[4]^[5]
綠鏽鹽酸鹽 - GR(Cl−
)：[Fe2+
3Fe3+
(HO−
)₈]⁺ · [Cl−
·nH
2O]⁻.^[4]^[5]^[6]
綠鏽硫酸鹽 - GR(SO2−
4)：[Fe2+
4Fe3+
2(HO−
)₁₂]²⁺ · [SO2−
4·2H
2O]²⁻.^[5]^[7]^[8]

其它文獻中還有這些陰離子的報道：Br−
、^[7]F−
、^[7]I−
、^[9]NO−
3^[10]和SeO2−
4^[11]。

綠鏽最初在鐵或鋼的表面被發現。^[2]它在自然界中也能以該礦物的形式存在。^[1]

製備

綠鏽可由含Fe(II)的溶液在SO₄^2-、CO₃^2-或Cl^-電漿的存在下，用氧化劑（如空氣、過氧化氫等）氧化，再用NaOH沉澱得到。^[12]

用途

綠鏽可用於一些有機物的降解。^[13]

參考文獻

[1]
J.-M. R. Génin, Ph. Refait, L. Simon, and S. H. Drissi (1998): "Preparation and Eh-pH diagrams of Fe(II)-Fe(III) green rust compounds; hyperfine interaction characteristics and stoichiometry of hydroxy-chloride, -sulphate and –carbonate". Hyperfine Interactions, volume 111, pages 313-318. doi:10.1023/A:1012638724990
[2]
P. P. Stampfl (1969): "Ein basisches Eisen II-III Karbonat in Rost. Corrosion Science 9, pages 185-187.
[3]
Hans C. B. Hansen (1989): "Composition, stabilization, and light absorption of Fe(II)Fe(III) hydroxy-carbonate ('green rust')". Clay Minerals, volume 24, pages 663-669. doi:10.1180/claymin.1989.024.4.08
[4]
M. Abdelmoula, Ph. Refait, S. H. Drissi, J. P. Mihe, and J.-M. R. Génin (1996): "Conversion electron Mössbauer spectroscopy and X-ray diffraction studies of the formation of carbonate-containing green rust one by corrosion of metallic iron in NaHCO3 and (NaHCO3 + NaCl) solutions". Corrosion Science, volume 38, pages 623-633. doi:10.1016/0010-938X(95)00153-B
[5]
M. Abdelmoula, F. Trolard, G. Bourrié and J.-M. R. Génin (1998): "Evidence of the Fe(II)–Fe(III) green rust `fougerite' mineral occurrence in a hydromorphic soil and its transformation with depth". Hyperfine Interactions, volume 111, pages 231-238. doi:10.1023/A:1010802508927
[6]
W. Feitknecht and G. Keller (1950): "Über die dunkelgrünen Hydroxyverbindungen des Eisens". Zeitschrift für anorganische und allgemeine Chemie, volume 262, pages 61-68. doi: 10.1002/zaac.19502620110
[7]
J. D. Bernal, D. R. Dasgupta, and A. L. Mackay (1959): "The oxides and hydroxides of iron and their structural inter-relationships". Clay Minerals Bulletin, volume 4, pages 15-30. doi:10.1180/claymin.1959.004.21.02
[8]
J.-M. R. Génin, A. A. Olowe, B. Resiak, N. D. Benbouzid-Rollet, M. Confente and D. Prieur (1993): "Identification of sulphated green rust 2 compound produced as a result of microbially induced corrosion of steel sheet piles in harbour". In Marine Corrosion of Stainless Steels: Chlorination and Microbial Effects, European Federation Corrosion Series, The Institute of Materials, London; volume 10, pages 162-166.
[9]
L. Vins, J. Subrt, V. Zapletal, and F. Hanousek (1987): "Preparation and properties of green rust type substances". Collect. Czech. Chem. Comm. volume 52, pages 93-102.
[10]
J. R. Gancedo, M. L. Martinez, and J. M. Oton (1983): "Formación de 'herrumbre verde' en soluciones de NH4NO3" (= "Formation of green rust in NH4NO3 solutions"). Anales de Química, Série A, volume 79, pages 470-472.
[11]
P Refait, L Simon, J-M R Génin. Reduction of SeO₄^2- Anions and Anoxic Formation of Iron(II)−Iron(III) Hydroxy-Selenate Green Rust. Environ. Sci. Technol., 2000, 34 (5), pp 819–825 DOI: 10.1021/es990376g
[12]
陳英, 吳德禮, 張亞雷等. 綠鏽的結構特徵與反應活性（頁面存檔備份，存於網際網路檔案館）[J]. 化工學報, 2014
[13]
徐楠楠，阮秀秀. 有機綠鏽對水體有機污染物的降解去除. 全國環境化學學術大會, 2013

[genin98-1] [1]
J.-M. R. Génin, Ph. Refait, L. Simon, and S. H. Drissi (1998): "Preparation and Eh-pH diagrams of Fe(II)-Fe(III) green rust compounds; hyperfine interaction characteristics and stoichiometry of hydroxy-chloride, -sulphate and –carbonate". Hyperfine Interactions, volume 111, pages 313-318. doi:10.1023/A:1012638724990

[stampfl69-2] [2]
P. P. Stampfl (1969): "Ein basisches Eisen II-III Karbonat in Rost. Corrosion Science 9, pages 185-187.

[hansen89-3] [3]
Hans C. B. Hansen (1989): "Composition, stabilization, and light absorption of Fe(II)Fe(III) hydroxy-carbonate ('green rust')". Clay Minerals, volume 24, pages 663-669. doi:10.1180/claymin.1989.024.4.08

[abdel96-4] [4]
M. Abdelmoula, Ph. Refait, S. H. Drissi, J. P. Mihe, and J.-M. R. Génin (1996): "Conversion electron Mössbauer spectroscopy and X-ray diffraction studies of the formation of carbonate-containing green rust one by corrosion of metallic iron in NaHCO3 and (NaHCO3 + NaCl) solutions". Corrosion Science, volume 38, pages 623-633. doi:10.1016/0010-938X(95)00153-B

[abdel98-5] [5]
M. Abdelmoula, F. Trolard, G. Bourrié and J.-M. R. Génin (1998): "Evidence of the Fe(II)–Fe(III) green rust `fougerite' mineral occurrence in a hydromorphic soil and its transformation with depth". Hyperfine Interactions, volume 111, pages 231-238. doi:10.1023/A:1010802508927

[feit50-6] [6]
W. Feitknecht and G. Keller (1950): "Über die dunkelgrünen Hydroxyverbindungen des Eisens". Zeitschrift für anorganische und allgemeine Chemie, volume 262, pages 61-68. doi: 10.1002/zaac.19502620110

[bernal59-7] [7]
J. D. Bernal, D. R. Dasgupta, and A. L. Mackay (1959): "The oxides and hydroxides of iron and their structural inter-relationships". Clay Minerals Bulletin, volume 4, pages 15-30. doi:10.1180/claymin.1959.004.21.02

[genin93-8] [8]
J.-M. R. Génin, A. A. Olowe, B. Resiak, N. D. Benbouzid-Rollet, M. Confente and D. Prieur (1993): "Identification of sulphated green rust 2 compound produced as a result of microbially induced corrosion of steel sheet piles in harbour". In Marine Corrosion of Stainless Steels: Chlorination and Microbial Effects, European Federation Corrosion Series, The Institute of Materials, London; volume 10, pages 162-166.

[vins87-9] [9]
L. Vins, J. Subrt, V. Zapletal, and F. Hanousek (1987): "Preparation and properties of green rust type substances". Collect. Czech. Chem. Comm. volume 52, pages 93-102.

[gancedo83-10] [10]
J. R. Gancedo, M. L. Martinez, and J. M. Oton (1983): "Formación de 'herrumbre verde' en soluciones de NH4NO3" (= "Formation of green rust in NH4NO3 solutions"). Anales de Química, Série A, volume 79, pages 470-472.

[11] [11]
P Refait, L Simon, J-M R Génin. Reduction of SeO₄^2- Anions and Anoxic Formation of Iron(II)−Iron(III) Hydroxy-Selenate Green Rust. Environ. Sci. Technol., 2000, 34 (5), pp 819–825 DOI: 10.1021/es990376g

[chen-12] [12]
陳英, 吳德禮, 張亞雷等. 綠鏽的結構特徵與反應活性（頁面存檔備份，存於網際網路檔案館）[J]. 化工學報, 2014

[13] [13]
徐楠楠，阮秀秀. 有機綠鏽對水體有機污染物的降解去除. 全國環境化學學術大會, 2013

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]

[10]

[11]

[12]

[13]