Featured paper: “Green” nanoparticles for water treatment.


The scientific paper by members of the Brazilian community on Materials research featured this month is: “Green” colloidal ZnS quantum dots/chitosan nano-photocatalysts for advanced oxidation processes: Study of the photodegradation of organic dye pollutants. Alexandra A.P. Mansur, Herman S. Mansur, Fábio P. Ramanery, Luiz Carlos Oliveira, Patterson P. Souza. Applied Catalysis B: Environmental158–159 (2014), 269–279. DOI:10.1016/j.apcatb.2014.04.026.

“Green” nanoparticles for water treatment

A group of researchers from Brazilian institutions developed nanoparticles that are triply “green”. They can be used to purify water, one the greatest global challenges of the 21st Century. In addition to that, they coexist harmonically with the environment and biological systems. Finally, they are produced by means of an eco-friendly process.

“We managed to integrate properties and characteristics rarely found in nanostructured systems, which are biocompatibility and environmental compatibility, using a ‘green’ process”, says Professor Herman Sander Mansur from the Federal University of Minas Gerais (UFMG).

The particles are formed by “quantum dots” (fluorescent semiconductor nanocrystals) of zinc sulfide (ZnS) with approximately 3.8 nm in size, coated with “shells” made of chitosan – an abundant, low-cost material, derived from the external skeleton of crustaceans such as shrimps and crabs. The synthesis process of these particles is completed in a single stage, carried out in an aqueous medium, without using toxic substances.

In a study performed by the research team, the nanoparticles displayed the capacity to degrade contaminant organic pigments usually found in water, using only light, including direct sunlight.

“The results were very promising, since we were able to observe that the system was effective for the photodegradation of organic contaminants found in the aqueous solutions we studied,” said Herman Mansur, who is the corresponding author of a paper about the research, recently released by the journal Applied Catalysis B: Environmental.

The research will also be the subject of a patent application, which the authors already started writing. “The following step will be searching potential partners in the private sector, in order to commercialize it as a product for cleaning waters which are polluted by organic pigments”, says Mansur.

Schematic representation of the nanostructured system produced with a ZnS core and chitosan shell for photodegradation of organic pollutants in water.

History of the paper

It was during scientific discussions occurred in the monthly meetings of the Exact Sciences and Materials Board of the Minas Gerais State Research Foundation (FAPEMIG) that the initial idea for the research came up.  In fact, both, Herman Mansur, coordinator of the UFMG Nanosciences, Nanotechnology and Innovation Center, and Luis Carlos de Oliveira, coordinator of the research group in Advanced Materials for Catalysis and Photocatalysis in the same university, were members of said advisory committee between February 2010 and the same month in 2014. According to Mansur, “the main idea was to use nanotechnology to develop innovative environmental solutions to clean up water, as it is an increasingly scarce resource in the world, whether in developed or emergent countries, as well as the ones with low social and economic development”.

Then, the professors prepared a project that combined the experience from the two research groups: Professor Mansur’s team, dedicated for twenty years to the development of nanomaterials and nanostructures by means of the synthesis of quantum dots, and Professor Oliveira’s group, which had been working in the field of chemical catalysis, searching sustainable solutions for the treatment of industrial waste.

Their initial research led to a first article on nanoparticles with cadmium sulfide (CdS) core and niobium oxide shell: L. C Oliveira et. al. One-pot Synthesis of CdS@Nb2O5 Core-Shell Nanostructures with Enhanced Photocatalytic ActivityApplied Catalysis. B, Environmental, v. 152:53, p. 403-412, 2014 (DOI:10.1016/j.apcatb.2014.01.025).

As a result, the group conceived, designed and developed an application for the concept of “green chemistry” in the whole project, producing zinc sulfide and chitosan particles, and their synthesis process. In the following stage, their research also incorporated the collaboration of Professor Patterson P. Souza, from the Federal Center for Technological Education of Minas Gerais (CEFET-MG), who conducted mass spectrometry tests, assessing the degradation of the organic pigments used as models for the polluting chemical species.

Featured paper: Changing the properties and morphology of graphene nanoribbons with nitrogen.


The scientific paper by members of the Brazilian community in Materials research featured this month is:

Josue Ortiz-Medina,  M. Luisa García-Betancourt,  Xiaoting Jia,  Rafael Martínez-Gordillo,  Miguel A. Pelagio-Flores,  David Swanson,  Ana Laura Elías,  Humberto R. Gutiérrez,  Eduardo Gracia-Espino,  Vincent Meunier, Jonathan Owens,  Bobby G. Sumpter, Eduardo Cruz-Silva,  Fernando J. Rodríguez-Macías,  Florentino López-Urías,  Emilio Muñoz-Sandoval, Mildred S. Dresselhaus,  Humberto Terrones,  Mauricio Terrones. Nitrogen-Doped Graphitic Nanoribbons: Synthesis, Characterization and Transport. Advanced Functional Materials 2013, 23, 3755-3762. DOI 10.1002/adfm.201202947.

Changing the properties and morphology of graphene nanoribbons with nitrogen

Multiple layers of graphene with the shape of ribbons (narrow and long) are called graphitic nanoribbons. These materials have been studied to control their properties by various methods, such as doping, in which are introduced atoms of “foreign” elements in the graphene carbon lattice.

In a study led by scientists at Pennsylvania State University with the participation of researchers from institutions in the United States, Mexico, Spain and Brazil, nitrogen-doped graphitic nanoribbons were manufactured by the chemical vapor deposition (CVD) method and showed new features, linked with the introduction of nitrogen, such as highest semiconductor performance, promising for applications in electronic devices, chemical reactivity and a very particular morphology on its edges.  The research was published in the journal Advanced Functional Materials.

“This article showed by the first time that it is possible to make doping with nitrogen on the same synthesis by CVD of graphite nanoribbons, and that you can control the level of doping during synthesis,” highlights Fernando Rodríguez-Macías, foreign visiting professor at the Brazilian Federal University of Pernambuco (UFPE) and one of the authors of the scientific paper. A Mexican national, Rodríguez-Macías came to UFPE in 2012, during his sabbatical year to work as a foreign visiting professor in the Department of Fundamental Chemistry and in the Graduate Program in Materials Science of the University. “I have prolonged my stay for another year to continue until 2014 doing collaborative studies for the production of carbon nanostructures, of bionanotechnology and toxicity of nanomaterials,” says the professor. “I am also teaching preparation and characterization of materials,” he adds.

The doped nanoribbons

The article’s authors showed that different concentrations of nitrogen generate controlled changes in material behavior. In particular, scientists have proven that the more nitrogen introduced into the structure of graphene, the most predominant the semiconductor behavior of nanoribbons. As an explanation to this phenomenon, the researchers suggested, based on theoretical calculations, that nitrogen atoms of doped nanoribbons act as scattering centers of electrons and decrease the conductive behavior of undoped graphene. “The control of doping level allows you to change the electrical properties of the nanoribbons, which can be useful for applications in transistors and other electronic devices,” says Rodríguez-Macías.

In addition, the paper also shows that the reactivity of nanoribbons can change with the doping level. Pure graphene, explains UFPE’s visiting professor, is very inert and has limited interactions with many chemical substances; on the other hand, nanoribbons doped with nitrogen are more reactive, which makes them useful for applications in sensors and catalysis.

As to the morphology, the article’s authors found that the nitrogen-doped nanoribbons have loops on their edges, uniting different graphene sheets. “This morphology is not presented by undoped graphite nanoribbons,” says Rodríguez-Macías.

This figure, sent by Professor Fernando Rodríguez-Macías, shows the nitrogen-doped graphitic nanoribbons in three scales. The scanning electron microscopy (top left corner) shows how these ribbons are made up of several layers and feature a curved surface with roughness. The transmission electronic microscopy (bottom left corner) shows that the nanoribbon layers are graphene sheets. The high resolution transmission electronic microscopy (right) shows that the layers of graphene on the nanoribbons edges form loops uniting different graphene sheets.

Collaborators

Almost all work of materials synthesis of the paper of Advanced Functional Materials was developed at Pennsylvania State University; the characterization was done in collaboration with other researchers and laboratories, reports UFPE’s visiting professor.

The participation of UFPE in the article happened through the doctoral student Miguel Angel Pelagio-Flores in the analysis and theoretical modeling of doped nanoribbons, and through professor Fernández-Macías himself, who, in addition to having participated in the discussion of results and review of the article from his office at UFPE, was doctoral advisor of the first author of the article, Josué Ortiz-Medina, while professor of a Mexican institution, IPICYT. “Ortiz-Medina did most of the experimental work of the article, besides being an important part of the characterization and theoretical studies of these new nanomaterials, when he was in exchange at Penn State in the laboratory of professor Terrones,” contextualizes the professor.

In total, 19 authors sign the article, among them MIT’s Professor Mildred Dresselhaus, reference in carbon science.

Artigo científico em destaque: Observação ao vivo da formação de nanofilamentos de prata por uma nova rota de síntese.


O artigo científico de membros da comunidade brasileira de pesquisa em Materiais em destaque neste mês é:

E. Longo, L. S. Cavalcante,D. P. Volanti, A. F. Gouveia, V. M. Longo, J. A. Varela, M. O. Orlandi and J. Andrés. Direct in situ observation of the electron-driven synthesis of Ag filaments on α-Ag2WO4 crystals. Scientific Reports 3, 2013, article number 1676. DOI: 10.1038/srep01676.

Texto de divulgação:
Observação ao vivo da formação de nanofilamentos de prata por uma nova rota de síntese

Quando, no Instituto de Química do campus de Araraquara da Unesp, o microscópio eletrônico de transmissão mostrou o crescimento de protuberâncias nanométricas nos bastões de tungstato de prata que estavam sendo analisados, a equipe de pesquisadores se surpreendeu bastante. Na verdade, os cientistas estavam estudando as propriedades fotoluminescentes dos cristais de tungstato, mas, dando sequência à investigação dessas protuberâncias e após repetir o experimento e caracterizar as amostras, eles acabaram concluindo que se tratava de nanofilamentos de prata, gerados a partir da matriz de tungstato. Os pesquisadores tinham descoberto uma rota de síntese inovadora para esse material, chamada de eletrossíntese por ser produzida por elétrons.

Esta sequência de imagens de microscopia eletrônica de transmissão obtidas de cinco em cinco segundos, reproduz aproximadamente o que os cientistas viram nessa oportunidade. A setinha azul mostra os nanofilamentos crescendo.

Imagens extraídas do artigo da Scientific Reports.

A eletrossíntese se baseia no fenômeno, conhecido para os iniciados e provavelmente surpreendente para os leigos, da interação dos elétrons emitidos pelos microscópios eletrônicos com os objetos que estão sendo observados. Nesses microscópios, sejam eles de transmissão (MET) ou de varredura (MEV), feixes de elétrons são direcionados para as amostras. Da interação entre ambos resultam códigos que acabam gerando imagens que ampliam os objetos observados em até milhões de vezes. Porém, como “efeito colateral”, a alta energia desses elétrons pode produzir modificações nos materiais observados, como, por exemplo, o desgaste das amostras.

No caso da pesquisa com tungstato de prata, o efeito colateral foi, além de surpreendente, positivo e construtivo, dando início a um avanço relevante para a Ciência e Engenharia de Materiais. A pesquisa gerou um artigo assinado por oito pesquisadores: sete brasileiros ligados à Unesp e à UFSCar, e participantes do Centro Multidisciplinar para o Desenvolvimento de Materiais Cerâmicos (CMDC), e um cientista da Universidade Jaume I, da Espanha. O paper foi publicado, em abril deste ano, na Scientific Reports, periódico de acesso aberto do grupo Nature lançado em 2011.

Importância da descoberta

Nanopartículas de prata têm aplicações de impacto, principalmente devido a suas propriedades bactericidas. De fato, revestimentos de prata são realizados, por meio de métodos de deposição, para impedir a proliferação de bactérias em diversos materiais. Nesse sentido, os nanofilamentos de prata gerados por eletrossíntese a partir do tungstato de prata são ainda mais interessantes, desde que a radiação os torna três vezes mais bactericidas do que materiais similares obtidos por outras rotas.

Alguns aspectos da fabricação dos nanofilamentos de prata via eletrossíntese podem ser controlados. Por exemplo, ao se aumentar a energia dos elétrons, aumenta também a velocidade de crescimento dos nanofilamentos. Por isso o uso de microscópios de transmissão é mais eficiente do que o de microscópios de varredura na síntese dos nanofilamentos.

Entretanto, além das aplicações deste novo material, o importante avanço inicial trazido por esta pesquisa feita no Brasil foi a possibilidade de observar o crescimento dos nanofilamentos in situ e em tempo real através dos mesmos microscópios eletrônicos que estavam promovendo seu crescimento. Os pesquisadores puderam analisar o processo de nucleação (formação inicial da nanopartícula de prata a partir do cristal de tungstato) e, em seguida, o crescimento dos nanofilamentos. Complementando essas observações com técnicas de caracterização de materiais, cálculos e teorias, os cientistas puderam apresentar uma explicação científica de por que o material se comporta dessa maneira.

A explicação, ou mecanismo de crescimento, se baseia na compreensão da estrutura dos cristais de tungstato de prata. Ao receberem a irradiação de elétrons, os diversos clusters que constituem os cristais (AgO4, AgO2, WO6 e outros) se desorganizam e reorganizam, ocorrendo transferências de elétrons por meio de reações de redução-oxidação (redox). Dessas reações surgem as nanopartículas de prata, que brotam na superfície dos cristais e crescem axialmente formando os nanofilamentos.