During the metabolism of organic matter (CH2O), sulfate-reducing bacteria (SRB) use sulfate
as the terminal electron acceptor, resulting in the production of H2S. This biologically
generated sulfide, in the presence of metal ions, can be used for metal precipitation (Bhagat et
al., 2004). The use of SRB in bioremediation processes, namely, in the reduction of highcontent
sulfate and metal effluents, is well documented (Costa and Duarte, 2005; Garcia et al.,
2001). Nevertheless, the process generates an excess of sulfide and the elimination of the
sulfide in excess and disposal of the metal sulfides produced are also problems that need to be
carefully addressed. Copper monosulfide (CuS) has gained considerable attention in material
science due to its excellent potential in catalysis (Mallick et al., 2007), optical functionality
(Liz-Marzan, 2006) and electronic functionalities (Kamat, 2002)

Costa, Maria Clara

Girão, Ana Violeta

Lourenço, J. P.

Monteiro, O. C.

Pinto da Costa, João

Trindade, Tito

Universidade do Algarve

4th International Conference on Engineering for Waste and Biomass Valorisation September 10-13, 2012 – Porto, Portugal 
USE OF BIOGENIC SULFIDE FOR THE SYNTHESIS OF CuS 
NANOCRYSTALS AND NANOCOMPOSITES. 
 
J. PINTO DA COSTA1, A. V. GIRÃO2, J. P. LOURENÇO3, O. C. MONTEIRO4, T. 
TRINDADE2, M. C. COSTA1,* 
1 Centro de Ciências do Mar, CCMar, Faculdade de Ciências e de Tecnologia, Campus de 
Gambelas, 8005-139 Faro, Portugal. 
1 Centro de Investigação em Materiais Cerâmicos e Compósitos, CICECO, Campus 
Universitário de Santiago, 3810-193 Aveiro, Portugal.  
3 Centro de Investigação em Química do Algarve, CIQA, Faculdade de Ciências e de 
Tecnologia, Campus de Gambelas, 8005-139  Faro, Portugal 
4Centro de Química e Bioquímica, CQB, Faculdade de Ciências Universidade de Lisboa, 
Campo Grande, 1749-016, Lisboa, Portugal. 
*Corresponding author: mcorada@ualg.pt, +351 289 800 900, Ext.: 7634. 
 
 
 
Abstract 
 
During the metabolism of organic matter (CH2O), sulfate-reducing bacteria (SRB) use sulfate 
as the terminal electron acceptor, resulting in the production of H2S. This biologically 
generated sulfide, in the presence of metal ions, can be used for metal precipitation (Bhagat et 
al., 2004). The use of SRB in bioremediation processes, namely, in the reduction of high-
content sulfate and metal effluents, is well documented (Costa and Duarte, 2005; Garcia et al., 
2001). Nevertheless, the process generates an excess of sulfide and the elimination of the 
sulfide in excess and disposal of the metal sulfides produced are also problems that need to be 
carefully addressed. Copper monosulfide (CuS) has gained considerable attention in material 
science due to its excellent potential in catalysis (Mallick et al., 2007), optical functionality 
(Liz-Marzan, 2006) and electronic functionalities (Kamat, 2002). Moreover, copper 
monosulfide shows metallic conductivity and transforms into superconductor at 1.6 K, 
exhibiting fast-ion conduction at high temperature (Yang and Xiang, 2005). In this work, we 
aimed for the valorization of these bioremediation by-products and have successfully used the 
biogenic sulfide produced by SRB for the production of well defined CuS nanocrystals 
(covellite) with a mean size of ∼3.5 nm. We also showed that the use of TiO2 and SiO2 as 
substrates resulted in the respective composite materials. Considering the growing interest of 
CuS nanoparticles in processes such as photocatalysis (Li et al., 2010; Stroyuk et al., 2004) 
and the simplicity of the process presented, this is a convenient route for the biological 
synthesis of functional materials with potential interest. 
 
 
4th International Conference on Engineering for Waste and Biomass Valorisation September 10-13, 2012 – Porto, Portugal 
References 
 
Bhagat, M., Burgess, J.E., Antunes, A.P.M., Whiteley, C.G. and Duncan, J.R., 2004. 
Precipitation of mixed metal residues from wastewater utilising biogenic sulphide. 
Minerals Engineering, 17(7-8): 925-932. 
Costa, M.C. and Duarte, J.C., 2005. Bioremediation of acid mine drainage using acidic soil 
and organic wastes for promoting sulphate-reducing bacteria activity on a column 
reactor. Water Air Soil Poll, 165(1-4): 325-345. 
Garcia, C., Moreno, D.A., Ballester, A., Blazquez, M.L. and Gonzalez, F., 2001. 
Bioremediation of an industrial acid mine water by metal-tolerant sulphate-reducing 
bacteria. Minerals Engineering, 14(9): 997-1008. 
Kamat, P.V., 2002. Photophysical, photochemical and photocatalytic aspects of metal 
nanoparticles. Journal of Physical Chemistry B, 106(32): 7729-7744. 
Li, F., Wu, J.F., Qin, Q.H., Li, Z. and Huang, X.T., 2010. Controllable synthesis, optical and 
photocatalytic properties of CuS nanomaterials with hierarchical structures. Powder 
Technol, 198(2): 267-274. 
Liz-Marzan, L.M., 2006. Tailoring surface plasmons through the morphology and assembly 
of metal nanoparticles. Langmuir, 22(1): 32-41. 
Mallick, K., Witcomb, M.J. and Scurrell, M.S., 2007. Self assembly of the metal 
nanoparticles: Formation of the highly oriented, core-shell type, bimetallic gold-silver 
film. J Nanopart Res, 9(2): 323-330. 
Stroyuk, A.L., Raevskaya, A.E., Kuchmii, S.Y. and Kryukov, A.I., 2004. Catalytic activity of 
CuS nanoparticles in hydrosulfide ions air oxidation. J Mol Catal a-Chem, 212(1-2): 
259-265. 
Yang, Y.J. and Xiang, J.W., 2005. Template-free synthesis of CuS nanorods with a simple 
aqueous reaction at ambient conditions. Appl Phys a-Mater, 81(7): 1351-1353. 
 
 


Use of biogenic sulfide for the synthesis of CuS nanocrystals and nanocomposites

Sapientia

4th International Conference on Engineering for Waste and Biomass Valorisation September 10-13, 2012 – Porto, Portugal USE OF BIOGENIC SULFIDE FOR THE SYNTHESIS OF CuS NANOCRYSTALS AND NANOCOMPOSITES.  J. PINTO DA COSTA1, A. V. GIRÃO2, J. P. LOURENÇO3, O. C. MONTEIRO4, T. TRINDADE2, M. C. COSTA1,* 1 Centro de Ciências do Mar, CCMar, Faculdade de Ciências e de Tecnologia, Campus de Gambelas, 8005-139 Faro, Portugal. 1 Centro de Investigação em Materiais Cerâmicos e Compósitos, CICECO, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal.  3 Centro de Investigação em Química do Algarve, CIQA, Faculdade de Ciências e de Tecnologia, Campus de Gambelas, 8005-139  Faro, Portugal 4Centro de Química e Bioquímica, CQB, Faculdade de Ciências Universidade de Lisboa, Campo Grande, 1749-016, Lisboa, Portugal. *Corresponding author: mcorada@ualg.pt, +351 289 800 900, Ext.: 7634.    Abstract  During the metabolism of organic matter (CH2O), sulfate-reducing bacteria (SRB) use sulfate as the terminal electron acceptor, resulting in the production of H2S. This biologically generated sulfide, in the presence of metal ions, can be used for metal precipitation (Bhagat et al., 2004). The use of SRB in bioremediation processes, namely, in the reduction of high-content sulfate and metal effluents, is well documented (Costa and Duarte, 2005; Garcia et al., 2001). Nevertheless, the process generates an excess of sulfide and the elimination of the sulfide in excess and disposal of the metal sulfides produced are also problems that need to be carefully addressed. Copper monosulfide (CuS) has gained considerable attention in material science due to its excellent potential in catalysis (Mallick et al., 2007), optical functionality (Liz-Marzan, 2006) and electronic functionalities (Kamat, 2002). Moreover, copper monosulfide shows metallic conductivity and transforms into superconductor at 1.6 K, exhibiting fast-ion conduction at high temperature (Yang and Xiang, 2005). In this work, we aimed for the valorization of these bioremediation by-products and have successfully used the biogenic sulfide produced by SRB for the production of well defined CuS nanocrystals (covellite) with a mean size of ∼3.5 nm. We also showed that the use of TiO2 and SiO2 as substrates resulted in the respective composite materials. Considering the growing interest of CuS nanoparticles in processes such as photocatalysis (Li et al., 2010; Stroyuk et al., 2004) and the simplicity of the process presented, this is a convenient route for the biological synthesis of functional materials with potential interest.   4th International Conference on Engineering for Waste and Biomass Valorisation September 10-13, 2012 – Porto, Portugal References  Bhagat, M., Burgess, J.E., Antunes, A.P.M., Whiteley, C.G. and Duncan, J.R., 2004. Precipitation of mixed metal residues from wastewater utilising biogenic sulphide. Minerals Engineering, 17(7-8): 925-932. Costa, M.C. and Duarte, J.C., 2005. Bioremediation of acid mine drainage using acidic soil and organic wastes for promoting sulphate-reducing bacteria activity on a column reactor. Water Air Soil Poll, 165(1-4): 325-345. Garcia, C., Moreno, D.A., Ballester, A., Blazquez, M.L. and Gonzalez, F., 2001. Bioremediation of an industrial acid mine water by metal-tolerant sulphate-reducing bacteria. Minerals Engineering, 14(9): 997-1008. Kamat, P.V., 2002. Photophysical, photochemical and photocatalytic aspects of metal nanoparticles. Journal of Physical Chemistry B, 106(32): 7729-7744. Li, F., Wu, J.F., Qin, Q.H., Li, Z. and Huang, X.T., 2010. Controllable synthesis, optical and photocatalytic properties of CuS nanomaterials with hierarchical structures. Powder Technol, 198(2): 267-274. Liz-Marzan, L.M., 2006. Tailoring surface plasmons through the morphology and assembly of metal nanoparticles. Langmuir, 22(1): 32-41. Mallick, K., Witcomb, M.J. and Scurrell, M.S., 2007. Self assembly of the metal nanoparticles: Formation of the highly oriented, core-shell type, bimetallic gold-silver film. J Nanopart Res, 9(2): 323-330. Stroyuk, A.L., Raevskaya, A.E., Kuchmii, S.Y. and Kryukov, A.I., 2004. Catalytic activity of CuS nanoparticles in hydrosulfide ions air oxidation. J Mol Catal a-Chem, 212(1-2): 259-265. Yang, Y.J. and Xiang, J.W., 2005. Template-free synthesis of CuS nanorods with a simple aqueous reaction at ambient conditions. Appl Phys a-Mater, 81(7): 1351-1353.   

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Use of biogenic sulfide for the synthesis of CuS nanocrystals and nanocomposites

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