Electrochemical behavior of hybrid carbon nanomaterials: the chemistry behind electrochemistry

Significance Statement

Synthesis of hybrid carbon nanomaterials synthesized by temperature-induced opening of multi-walled carbon nanotubes (MWCNTs) has yielded three types of multi-walled carbon nanotubes and graphene oxide nanoribbons (GONRs) hybrids. Graphene oxide nanoribbons are basically unzipped multi-walled carbon nanotubes. The main synthesis challenge is the production temperature, which is a critical parameter for the oxygen functional group formation, and determines their electronic structure and their electrochemical performance.

Researcher teams led by Professor Alberto Escarpa from University of Alcala and Professor M. Teresa Martínez at Instituto de Carboquimica ICB-CSIC in Spain proposed to investigate the electrochemical behavior of hybrid carbon nanomaterial production. Their aim was to control the chemistry involved in the production process of nanomaterials, thereby improving the electrochemical performance, which could lead to advanced materials for specific molecular detection. Their work is now published in the peer-reviewed journal Electrochimica Acta

At first, the research team synthesized carbon hybrid nanomaterials by unzipping commercially available MWCNTs at three different temperatures 55 °C, 65 °C and 75 °C, yielding three graphene nanohybrids.

The synthesized carbon nanomaterials were fully characterized by different techniques, such as XRD, Raman, FTIR, XPS and TEM to establish the structural differences according to the different processing temperatures. It was determined that the oxidation degree increases with the production temperature.

Then, electrochemical and impedance measurements were conducted for a wide range of target molecules, at standard temperature, on an electrochemical workplace using a tri-electrode system with a platinum wire, silver-silver chloride and a glassy carbon electrodes.

The team concluded that by controlling chemical oxidation of multi-walled carbon nanotubes, which generates graphene oxide nanoribbons, new gates are opened leading to exploitation of carbon nanomaterials, as novel materials for both electrochemical sensing and biosensing of relevant target molecules. GONR at 65º C yielded promising revelations by containing specific moieties of suitable electrochemical features, which display amazing analytical performance in electrochemical sensing of varying structure chemical molecules. According to the structural analysis, the electrochemical behavior seems to be associated to the progress of the unzipping reaction that influences the balance between the Csp2/Csp3 ratio, the graphitic fraction and the type of functional groups introduced.

These results exhibit the importance of temperature in the production process, for tailoring a carbon nanomaterial that could be utilized in a specific molecular detection application shedding light into new possibilities for electrochemical sensing applications. It also guides the process to the production of advanced materials to be utilized in a specific molecular detection application.

There is a requirement for advanced renewable energy source technologies in order to meet the long term energy demand challenge and protect the environmental balance. Carbon nanomaterials have great potential to advance renewable energy and supercapacitor technologies. One example is employing and modifying carbon nanotubes as electrodes to increase power production in microbial fuel cells because of their high conductivity and large surface area. This provides an opportunity for the participation of carbon nanomaterials, especially in biofuel cells. Moreover, major breakthrough contributed by carbon nanomaterials in the solar energy sector lies in their application in photovoltaic devices. The new tools and improved synthesis of graphene oxide nanoribbons generated in this study provide an excellent nanomaterial to be used as hole or electron transfer layer in solar cells.

Electrochemical behavior of hybrid carbon nanomaterials the chemistry behind electrochemistry - Renewable Global Energy Innovations

About the author

Aida Martín is a postdoctoral researcher in Nanoengineering and Biology departments at University of California, San Diego, USA since 2016. Her research interests devotes to wearable sensing and biosensing, microfluidics, micro/nanomachines and electrochemical techniques for bacteria sensing in Pr. J. Wang and Pr. J. Hasty’s groups, respectively. She received his PhD. from the University of Alcala, Spain in 2016 where she worked with graphene and carbon nanomaterials for electroanalysis and using microfluidic techniques under the supervisión of Pr. A. Escarpa. She was also a visitor scholar at University of California San Diego in 2014-2015 where she was immersed into micro and nanomachine technologies.

She is co/author of 20 international papers, one international patent in disposable electrodes based on conducting nanomaterials and one book chapter in carbon nanomaterials for microfluidics.

About the author

Dr. Alberto Escarpa is Professor of Analytical Chemistry at the University of Alcalá since 2003. He has received several awards such the prestigious NATO post-doctoral Scholarship as postdoc researcher at the New Mexico State University (USA) in 2001 or the “Young Investigator Award” by the University of Alcala in 2003. He is the leader and founder of the group “Analytical Miniaturization and Nanotechnology” since 2003. His research activity is focused on microfluidics, biosensing, nanomaterials and micro motors.

He has co-authored more than 110 peer-reviewed articles in international journals, yielding an h-index of 33, is the editor of the book “Miniaturization of analytical systems: principles, designs and applications” (Wiley, 2009) and “Food Electroanalysis” (2015, Wiley). He has given more than 20 invited talks in highly international meetings about microfluidics and miniaturization of analytical chemistry. He is also Associate Editor of RSC Advances and Electrophoresis and member of the Editorial board of Electrophoresis, Food Chemistry, Applied Materials Today and Microchimica Acta. He is also member of Royal Society of Chemistry since 2016.

About the author

Alejandro Ansón Casaos was born in Zaragoza in 1978. He obtained his PhD in Physical Chemistry from the University of Zaragoza in June 2005 and is a Research Scientist at Instituto de Carboquimica ICB-CSIC since August 2012. His current research includes fundamentals and applications of carbon nanomaterials, mainly carbon nanotubes and graphene oxide, and their colloids. Most specifically, he is interested in the study of physicochemical properties that are relevant for applications in photocatalysis, photovoltaics, energy storage, sensors, and polymer composites. He likes music, chess, pelota, fitness activities, playing the saxophone, and reading essays, biographies and classical novels.

About the author

María del Carmen Marín was born in Quesada, in the south of Spain, and studied Chemistry at the University of Jaén. Afterwards, she moved to the University of Alcalá (Madrid) and completing her Master in Characterization of Chemical Systems in 2015. Her research in the group of Prof. Escarpa, involving the development of new materials modified with hybrid nanomaterials. Her results revelated the important of the temperature in the synthesis process. This opened the new opportunities for the electrochemical sensing and biosensing applications.

She is now a PhD student at the University of Siena (Italy) in the group of Prof. Olivucci. The investigation line is the developing a prototype protocol for the automatic and faster construction of congruous sets of QM/MM models of rhodopsin-like photoreceptors and of their mutants. The main application is the prediction of the vertical excitation energies for different set of rhodopsins. This project gave her the opportunity to collaborate with the Laboratory for Computational Photochemistry and Photobiology at the Bowling Green State University (EEUU) in 2016.

About the author

M. Teresa Martinez graduated in Chemistry (1976) and Chemical Engineering (1978) and received her PhD degree in the field of Chemistry from Zaragoza University in 1982. Currently she is Research Professor at the Institute of Carbon- Chemistry (CSIC) where she previously worked as CSIC Research Fellow and Senior Research Scientist. For the period 2002 to 2006 she became the director of the Institute of Carbon-Chemistry and from 1995 to 2014 she has led the group of Carbon Nanotubes and Nanotechnology. She has worked as visiting Professor in International Research Institutions ; 1989 Clausthal-Zellerfeld University (Germany), 1995 University of Sussex (UK), 2006-2007 Molecular Foundry (Lawrence Berkeley National Laboratory USA), 2008 Electrical Engineering and Computer Science California University at Berkeley(USA) and University of Santiago de Chile ( 2010).

Concerning specific and inter-personal competencies, she was a member of the European Coal and Steel Experts Committee for “Coal Conversion Area” (2000-2002) and co-chairman of the “Strategic Research Area” of the Hydrogen Platform for the VI Framework Programme 2004). At National level she has been a member of the Research and Development Advisory Committee of the Regional Government for the period 2004-2014 and a member of the CSIC Chemical Science and Technologies Area during the years 2001-2006.

Prof. Martinez has developed her research career in a multidisciplinary sphere in the field of material science, energy and environment and for the last 20 years she has approached these fields from the Nanotechnology developing nanomaterials for Energy, Enviromental and Biotechnological applications. Prof. Martinez research is focused on Nanoscience and Nanotechnology, her expertise is the development of materials (synthesis, functionalization and processing of hybrid and compounds materials) based on carbon nanostructures; carbon nanotubes, graphene and graphene quantum dots. The starting point was the pioneering work on the single walled carbon nanotubes production by CO2 Laser (1998) later complemented by CVD and arc-discharge techniques. Today Prof. Martinez and her group (Carbon Nanostructures and Nanotechnology founded in 1995) develop innovative and high quality research at the forefront of science combining physics, chemistry and engineering approaches fostering interdisciplinary research. She is so far, the co-author of over than 200 peer-reviewed publications and hundreds of communications to International Congress in these fields.

About the author

Dra. María Moreno Guzmán received her degree in Chemistry from the Complutense University of Madrid (Spain) in 2008 and her PhD in Chemistry from the Complutense University of Madrid (Spain) in 2013. The project was aimed to develop new miniaturized systems for multiplexed detection using functionalized artificial micro/nanosensors modified with different receptors. The research line focused on the development of artificial nano- and microsensors for analytical and environmental applications.

In 2015 she was moved with the prestigious group MINYNANOTECH (Analytical miniaturization and nanotechnology), under the mentorship of Dr. Escarpa at University of Alcalá, which allowed her to investigate a pioneer and new nanomotors research line with promising applications in the biomedical and analytical fields. Since then, she has participated in more than 7 research projects. She has co-authored over 17 scientific articles in international journals, written 1 book chapter and 21 international communications in national and international conferences. She has an H-index of 8.

She has both theoretical and practical expertise in nanomaterials microfabrication and characterization techniques. She has seven years of experience in developing pioneering methods for the determination of emerging contaminants in environmen and food.

About the author

Tania Sierra Gómez was born in Madrid, Spain. She studied Chemistry at the University of Alcalá (Madrid). After she completing her Master in Science Research in the specialty of Chemistry in 2016. Her research in the group of Prof. Escarpa, involving the exploration of different nanomaterials and their possible application for electrochemical sensing and biosensing.

She is now a PhD student at the University of Alcalá (Madrid) in the group of Prof. Escarpa. The investigation line is the developing protocol for the determination quickly and a low cost of biomarkers based on glycoproteins for application in diagnosis and evolution of the cancer.


María Moreno-Guzman1, Aída Martín1, María del Carmen Marín1, Tania Sierra1, Alejandro Ansón-Casaos2, María Teresa Martínez2, Alberto Escarpa1. Electrochemical behavior of hybrid carbon nanomaterials: the chemistry behind electrochemistry Electrochimica Acta volume 214 (2016) pages 286–294.

Show Affiliations
  1. Department of Analytical Chemistry, Physical Chemistry and Chemical Engineering, University of Alcala, E-28871, Alcalá de Henares, Spain
  2. Instituto de Carboquímica ICB-CSIC, Miguel Luesma Castán, 4, E-50018, Zaragoza, Spain


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