Featured paper: Nanostructured catalysts for renewable energy production.


Transmission electron microscopy image of electrocatalyst material: metallic nanoparticles encapsulated in carbon layers.
Transmission electron microscopy image of electrocatalyst material: metallic nanoparticles encapsulated in carbon layers.

Research carried out at the São Carlos Institute of Chemistry at the University of São Paulo (IQSC-USP) resulted in a nanostructured material that works as a catalyst for electrochemical reactions (electrocatalyst) that are fundamental in some renewable energy generation systems. As it combines efficiency and low cost, the new material would be an alternative to the catalysts traditionally used in these reactions, which are based on elements of the group of precious metals, such as platinum, which are scarce and expensive.

The developed material, which, with the naked eye, has the appearance of a black powder, is hybrid and nanostructured. It consists of nanoparticles from 10 to 50 nm, composed of an iron, cobalt and nickel alloy (three relatively abundant and cheap elements), inserted in layers of carbon doped with nitrogen.

Recently reported in the Journal of Materials Chemistry A, the study presents a very simple process to obtain this material with the necessary stability for electrocatalysis applications. The method consists of preparing a water solution with iron, cobalt and nickel salts and adding organic compounds capable of binding metal ions (so-called ligands). The reaction between metals and ligands generates structures known as MOFs (metal-organic frameworks). Eventually, the obtained MOFs are submitted to high temperature (900 ° C) to obtain the final material.

“We have come up with a unique straightforward yet effective strategy for synthesis of an efficient electrocatalyst that is cheap and quite active in diver’s energy conversion reactions and could have impact in new generation energy related technologies,” says Mohmmad Khalid, a postdoctoral fellow at the Electrochemistry Group at IQSC-USP and corresponding author of the article with Professor Hamilton Varela (IQSC-USP).

The article also reports the tests carried out at the laboratories of the Electrochemistry Group at IQSC-USP to assess the performance of the nanostructured material in some applications related to sustainable energy generation, such as the division of the water molecule (hydrolysis). This process is the cleanest way to obtain hydrogen, currently considered the most promising non-fossil fuel. However, without the participation of good electrocatalysts, hydrolysis is very slow and consumes a lot of electricity. “Our nanostructured catalyst in overall water splitting impeccably works for decomposing apart the water molecules for the generation of hydrogen at applying very low potential compare to several previously reported nonprecious electrocatalysts,” says Khalid.

The nanostructured material also showed very good results as a catalyst for ethanol oxidation. This reaction is carried out on direct ethanol fuel cells to obtain electrical energy from the chemical energy of ethanol (renewable fuel with Brazil as the second largest producer in the world). “Thus, the catalyst showed its potential not only to generate hydrogen, but also for fuel cell applications,” says Khalid.

Overcoming the challenges

The work began in 2017, with a research project coordinated by Professor Hamilton Brandão Varela de Albuquerque, with the participation of postdoctoral fellow Mohmmad Khalid. According to Khalid, the final objective of the study was to find a cheap and stable electrocatalyst for the process of dividing the water molecule.

The main problems the researchers faced were the aggregation of nanoparticles during the synthesis of the material and its dissolution in the electrolytes during the electrochemical tests. “The interesting idea came up with brain-storming discussion of Dr. Ana Maria Borges Honorato and after multiphases optimizing conditions of synthesis process,” says Khalid. In the material obtained, the carbon layers protect the catalyst nanoparticles and influence the material’s catalytic performance, which is affected by the thickness of these layers and by small variations in their composition. “This nanostructure allowed us to solve not only the problem of particle aggregation during synthesis and the problem of metal segregation/dissolution in electrolytes during the operation, but also to improve the catalytic performance in oxygen reduction, oxygen evolution, hydrogen evolution, ethanol oxidation reactions and general water division, with very competitive values in relation to reference catalysts,” summarizes the postdoctoral fellow.

The work received funding from Brazilian agencies CAPES, CNPq and FAPESP (São Paulo).

Main authors of the paper:  Mohmmad Khalid, Ana Maria Borges Honorato and Hamilton Varela.
Main authors of the paper: Mohmmad Khalid, Ana Maria Borges Honorato and Hamilton Varela.

[Paper: Trifunctional catalytic activities of trimetallic FeCoNi alloy nanoparticles embedded in a carbon shell for efficient overall water splitting. Mohd. Khalid, Ana M. B. Honorato,  Germano Tremiliosi Filho and  Hamilton Varela. J. Mater. Chem. A, 2020,8, 9021-9031.]

Featured paper. Super efficient nanoparticles to catalyze production of hydrogen, an alternative fuel.


[Paper: Hybrid tantalum oxide nanoparticles from the hydrolysis of imidazolium tantalate ionic liquids: efficient catalysts for hydrogen generation from ethanol/water solutions. Virgínia S. Souza, Jackson D. Scholten, Daniel E. Weibel, Dario Eberhardt, Daniel L. Baptista, Sérgio R. Teixeira and Jairton Dupont. J. Mater. Chem. A, 2016, 4, 7469-7475. DOI: 10.1039/C6TA02114J.]

Super efficient nanoparticles to catalyze production of hydrogen, an alternative fuel.

While some automobiles which use hydrogen fuel are entering the market, scientists from around the world are still trying to find cleaner, more sustainable, safer and cost-effective ways to generate and store hydrogen. In fact, even though it is the most abundant element in the universe and found in the water and in numerous other compounds, hydrogen cannot actually be found in its pure form on our planet. It must therefore be obtained from other chemical compounds.

One of the best methods to produce hydrogen, from ecological and economical points of view, is water splitting. This technique consists of separating water molecules into its two primary elements, generating hydrogen (H2) and oxygen (O2) gases. This separation can be achieved through the use of the abundant solar energy, at room temperature. However, in practice, for sunlight to split one water molecule, it requires nanoparticles made of semiconducting materials to act as catalysts, or more specifically, as photocatalysts.

In a study fully carried out in Brazil, a team of scientists developed a new simple and efficient method to produce tantalum oxide nanoparticles (Ta2O5) with outstanding performance catalysts for hydrogen generation. The research was reported in a paper recently published in the Journal of Materials Chemistry A (impact factor: 8.262).

Fotos dos autores principais do artigo. Começando pela esquerda do leitor: a doutora Virgínia Souza, o professor Jackson Scholten e o professor Jairton Dupont.
Picture of the main authors of the paper. From left to right: PhD Virgínia Souza, Prof. Jackson Scholten and Prof. Jairton Dupont.

This study was funded by the Brazilian research agencies CAPES and CNPq, as the doctoral research of Virgínia Serra Souza at the Chemistry Institute of the Federal University of Rio Grande do Sul (IQ-UFRGS), under the guidance of Professor Jairton Dupont.

“The idea for this research came when we were looking for an alternative and efficient route for the synthesis of Ta2O5 nanoparticles, and after some experiments we decided to test the possibility of using ionic liquids as stabilizing sources and agents of the nanomaterials”, says Professor Jackson Damiani Scholten, who is one of the corresponding authors of the paper and member of the research group of IQ-UFRGS. This group has extensive experience in the study and development of ionic liquids (salts which are in liquid state at room temperature). Due to their physicochemical properties, ionic liquids can be used in the preparation of nanoparticles as stabilizers to keep the particles in the nanometric range.

Souza, Scholten and Dupont prepared two types of ionic liquids containing tantalum and create the conditions for the hydrolysis reaction (breaking the chemical bonds of a compound by the addition of water). The elements resulting from the hydrolysis, from the water and the ionic liquid, recombine to form tantalum oxide nanoparticles.

The team realized it had produced tantalum oxide nanoparticles ranging between 1.5 and 22 nm, the smaller ones had been generated from one of the ionic liquids and the larger ones from the other. With the assistance of Professor Daniel E. Weibel, also from IQ-UFRGS, they studied the surface composition of the nanoparticles. These scientists proposed that the nanoparticles obtained were hybrid: remains of ionic liquid were observed around the tantalum oxide.

To see how the nanoparticles behaved as catalysts in the separation of water molecules to generate hydrogen, the team conducted photocatalytic tests at the facilities of the Institute of Physics – UFRGS, provided by Professor Sérgio R. Teixeira. The tests were carried out in a solution that besides water contained ethanol – a compound that helps to increase the hydrogen production rate.

“We were delighted that the Ta2O5 nanoparticles showed one of the best results ever published for the production of H2 from a water/ethanol solution”, recalls Professor Scholten. In the article, this exceptional result was attributed to the presence of ionic liquid in the nanoparticles. “We believe that the residual ionic liquid enhances the formation of a hydrophilic regions on the surface of Ta2O5, favoring the approximation of polar molecules (water and ethanol)”, explains Scholten. To be certain about this, the scientists removed the ionic liquid from the nanoparticles by heat treatment and confirmed their very low photocatalytic activity.

In another stage of the research, Dario Eberhardt, then professor at the University of Caxias do Sul (UCS), collaborated with the team in the deposition of roughly 1 nm platinum nanoparticles on the surface of the hybrid tantalum oxide nanoparticles by the sputtering technique, carried out at IF-UFRGS. Professor Daniel L. Baptista, of IF-UFRGS, helped to characterize the material. In the tests, the performance of the tantalum oxide nanoparticles with photocatalytic ionic liquid was even better with the addition of platinum.

This work, carried out in southern Brazil, presented a new method to produce super-efficient catalysts for hydrogen production, a promising alternative fuel from water and ethanol, two renewable and abundant resources.

This image provided by the authors of the paper exhibits the process to produce tantalum oxide nanoparticles from the hydrolysis of ionic liquids, followed by the deposition of platinum nanoparticles on the first material, and the application of the second material to obtain hydrogen gas in the “water splitting” process.
This image provided by the authors of the paper exhibits the process to produce tantalum oxide nanoparticles from the hydrolysis of ionic liquids, followed by the deposition of platinum nanoparticles on the first material, and the application of the second material to obtain hydrogen gas in the “water splitting” process.