Pedro Alves da Silva Autreto
Possui graduação em Física pela Universidade Estadual Paulista Júlio de Mesquita Filho (2004), mestrado em Física pela Universidade Estadual de Campinas (2007) e doutorado sanduíche pela Universidade Estadual de Campinas (2011) e University of Cambridge (Inglaterra). Tem experiência na área de Física, com ênfase em Estrutura Eletrônica de Átomos e Moléculas; Teoria, atuando principalmente nos seguintes temas: graphene, molecular dynamics, reaxff, lammps e nanofios. Fez pos-doutoramento na Universidade de Campinas (Unicamp) no estudo das propriedades eletrônicas e mecânicas de de nanoestruturas 2D, na Universidade de Rice (Houston, Estados Unidos), na área de dinâmica molecular reativa de nanoestruturas hibridas e na Universidade do ABC. Foi professor visitante nesta na Universidade Federal do ABC e atualmente é professor adjunto nesta universidade
2024
Quispe, Juan Gomez; Ipaves, Bruno; Galvao, Douglas Soares; da Silva Autreto, Pedro Alves
TPDH-Graphene as a New Anodic Material for Lithium Ion Battery: DFT-Based Investigations Journal Article
Em: ACS Omega, vol. 9, iss. 37, pp. 39195–39201, 2024.
Resumo | Links | BibTeX | Tags:
@article{nokey,
title = {TPDH-Graphene as a New Anodic Material for Lithium Ion Battery: DFT-Based Investigations},
author = {Juan Gomez Quispe and Bruno Ipaves and Douglas Soares Galvao and Pedro Alves da Silva Autreto
},
url = {https://pubs.acs.org/doi/full/10.1021/acsomega.4c06252},
doi = {4c06252},
year = {2024},
date = {2024-09-03},
urldate = {2024-09-03},
journal = {ACS Omega},
volume = {9},
issue = {37},
pages = {39195–39201},
abstract = {The potential of tetra-penta-deca-hexagonal graphene (TPDH-gr), a recently proposed 2D carbon allotrope as an anodic material in lithium ion batteries (LIBs), was investigated through density functional theory calculations. The results indicate that Li-atom adsorption is moderate (around 0.70 eV), allowing for easy desorption. Moreover, energy barriers (0.08–0.20 eV), diffusion coefficient (>6 × 10–6 cm2/s), and open circuit voltage (0.29 V) calculations show rapid Li atom diffusion on the TPDH-gr surface, stable intercalation of lithium atoms, and good performance during the charge and discharge cycles of the LIB. These findings, combined with the intrinsic metallic nature of TPDH-gr, indicate that this new 2D carbon allotrope is a promising candidate for use as an anodic LIB material.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The potential of tetra-penta-deca-hexagonal graphene (TPDH-gr), a recently proposed 2D carbon allotrope as an anodic material in lithium ion batteries (LIBs), was investigated through density functional theory calculations. The results indicate that Li-atom adsorption is moderate (around 0.70 eV), allowing for easy desorption. Moreover, energy barriers (0.08–0.20 eV), diffusion coefficient (>6 × 10–6 cm2/s), and open circuit voltage (0.29 V) calculations show rapid Li atom diffusion on the TPDH-gr surface, stable intercalation of lithium atoms, and good performance during the charge and discharge cycles of the LIB. These findings, combined with the intrinsic metallic nature of TPDH-gr, indicate that this new 2D carbon allotrope is a promising candidate for use as an anodic LIB material.
Slathia, Surbhi; Ipaves, Bruno; de Oliveira, Caique Campos; Negedu, Solomon Demiss; Sarkar, Suman; da Silva Autreto, Pedro Alves; Tiwary, Chandra Sekhar
Ultralow Detection of Mancozeb Using Two-Dimensional Cobalt Telluride (CoTe2) Journal Article
Em: Langmuir, vol. 40, iss. 30, pp. 15731–15740, 2024.
Resumo | Links | BibTeX | Tags:
@article{nokey,
title = {Ultralow Detection of Mancozeb Using Two-Dimensional Cobalt Telluride (CoTe2)},
author = {Surbhi Slathia and Bruno Ipaves and Caique Campos de Oliveira and Solomon Demiss Negedu and Suman Sarkar and Pedro Alves da Silva Autreto and Chandra Sekhar Tiwary},
url = {https://pubs.acs.org/doi/full/10.1021/acs.langmuir.4c01549},
doi = {4c01549},
year = {2024},
date = {2024-07-15},
urldate = {2024-07-15},
journal = {Langmuir},
volume = {40},
issue = {30},
pages = {15731–15740},
abstract = {Pesticides are crucial in modern agriculture because they reduce pests and boost yield, but they also represent major risks to human health and the environment; therefore, it is important to monitor their presence in food. Reliable and precise detection techniques are possible ways to address this issue. In this work, we utilize atomically thin (two-dimensional) cobalt telluride (CoTe2) with a high surface area and charge as a template material to detect mancozeb using spectroscopic and electrochemical techniques. When mancozeb (MNZ) molecules interact with 2D CoTe2, spectroscopic analyses reveal distinctive spectral shifts that clarify the underlying chemical interactions and binding mechanisms. Furthermore, CoTe2’s electroactive sites and their manipulation for improved sensitivity and selectivity toward certain MNZ molecules are investigated by electrochemical studies. The CoTe2/GCE electrode exhibits enhanced electrochemical activity toward the electrooxidation of MNZ. The developed sensing electrode shows a linear range from 0.184 mM to 18.48 μM and a limit of detection of about 0.18 μM. In addition, we employ density functional theory (DFT) first-principles calculations to validate the experimental findings and comprehend the mechanism behind the interaction between CoTe2 and MNZ molecules. The study highlights the effectiveness of 2D CoTe2 as a dual-mode sensing platform for qualitative and quantitative assessment of MNZ pollutants, demonstrated by the integration of electrochemistry and spectroscopy and the critical role that 2D CoTe2-based sensors can play in accurate and efficient pesticide detection, which is required for agricultural safety protocols and environmental monitoring.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Pesticides are crucial in modern agriculture because they reduce pests and boost yield, but they also represent major risks to human health and the environment; therefore, it is important to monitor their presence in food. Reliable and precise detection techniques are possible ways to address this issue. In this work, we utilize atomically thin (two-dimensional) cobalt telluride (CoTe2) with a high surface area and charge as a template material to detect mancozeb using spectroscopic and electrochemical techniques. When mancozeb (MNZ) molecules interact with 2D CoTe2, spectroscopic analyses reveal distinctive spectral shifts that clarify the underlying chemical interactions and binding mechanisms. Furthermore, CoTe2’s electroactive sites and their manipulation for improved sensitivity and selectivity toward certain MNZ molecules are investigated by electrochemical studies. The CoTe2/GCE electrode exhibits enhanced electrochemical activity toward the electrooxidation of MNZ. The developed sensing electrode shows a linear range from 0.184 mM to 18.48 μM and a limit of detection of about 0.18 μM. In addition, we employ density functional theory (DFT) first-principles calculations to validate the experimental findings and comprehend the mechanism behind the interaction between CoTe2 and MNZ molecules. The study highlights the effectiveness of 2D CoTe2 as a dual-mode sensing platform for qualitative and quantitative assessment of MNZ pollutants, demonstrated by the integration of electrochemistry and spectroscopy and the critical role that 2D CoTe2-based sensors can play in accurate and efficient pesticide detection, which is required for agricultural safety protocols and environmental monitoring.
Chakraborty, Anyesha; Ipaves, Bruno; de Oliveira, Caique Campos; Negedu, Solomon Demiss; Sarkar, Suman; Lahiri, Basudev; da Silva Autreto, Pedro Alves; Tiwary, Chandra Sekhar
Subpicomolar Dopamine Detection Using Two-Dimensional Cobalt Telluride Journal Article
Em: ACS Applied Engineering Materials, vol. 2, iss. 7, pp. 1935–1947, 2024.
Resumo | Links | BibTeX | Tags:
@article{nokey,
title = {Subpicomolar Dopamine Detection Using Two-Dimensional Cobalt Telluride},
author = {Anyesha Chakraborty and Bruno Ipaves and Caique Campos de Oliveira and Solomon Demiss Negedu and Suman Sarkar and Basudev Lahiri and Pedro Alves da Silva Autreto and Chandra Sekhar Tiwary},
url = {https://pubs.acs.org/doi/full/10.1021/acsaenm.4c00321},
doi = {4c00321},
year = {2024},
date = {2024-07-11},
journal = {ACS Applied Engineering Materials},
volume = {2},
issue = {7},
pages = {1935–1947},
abstract = {To address the challenges associated with ultrasensitive dopamine sensing for regular health monitoring, here we developed a flexible sensor using two-dimensional cobalt telluride (2D CoTe2). The 2D-CoTe2-coated glassy carbon electrode sensor shows a limit of detection (LoD) of 0.21 pM measured by differential pulse voltammetry (DPV) in 0.1 M phosphate buffer solution (PBS). The assessment of selectivity, repeatability, and reproducibility has been conducted, to enquire about the efficiency of the sensor. The durability of the sensor has been verified for a duration of one month, demonstrating a minimal loss of 16% after a period of one month. The interaction of the 2D CoTe2 and dopamine has been investigated thoroughly by chemical fingerprints using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and Raman imaging, and the adsorption of dopamine on 2D CoTe2 has been confirmed by the theoretical calculations calculating the binding energy, differential charge densities, and projected density of states (pDOS). Additionally, a flexible paper-based sensor using 2D CoTe2 has been successfully fabricated and employed for real-time dopamine detection from artificial sweat, which achieved a LoD of 0.22 pM.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
To address the challenges associated with ultrasensitive dopamine sensing for regular health monitoring, here we developed a flexible sensor using two-dimensional cobalt telluride (2D CoTe2). The 2D-CoTe2-coated glassy carbon electrode sensor shows a limit of detection (LoD) of 0.21 pM measured by differential pulse voltammetry (DPV) in 0.1 M phosphate buffer solution (PBS). The assessment of selectivity, repeatability, and reproducibility has been conducted, to enquire about the efficiency of the sensor. The durability of the sensor has been verified for a duration of one month, demonstrating a minimal loss of 16% after a period of one month. The interaction of the 2D CoTe2 and dopamine has been investigated thoroughly by chemical fingerprints using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and Raman imaging, and the adsorption of dopamine on 2D CoTe2 has been confirmed by the theoretical calculations calculating the binding energy, differential charge densities, and projected density of states (pDOS). Additionally, a flexible paper-based sensor using 2D CoTe2 has been successfully fabricated and employed for real-time dopamine detection from artificial sweat, which achieved a LoD of 0.22 pM.
Quispe, Juan Gomez; Galvao, Douglas Soares; da Silva Autreto, Pedro Alves
Exploring the Electronic and Mechanical Properties of TPDH-Nanotube: Insights from Ab initio and Classical Molecular Dynamics Simulations Journal Article
Em: ACSOmega, pp. 15, 2024.
Resumo | Links | BibTeX | Tags:
@article{nokey,
title = {Exploring the Electronic and Mechanical Properties of TPDH-Nanotube: Insights from Ab initio and Classical Molecular Dynamics Simulations },
author = {Juan Gomez Quispe and Douglas Soares Galvao and Pedro Alves da Silva Autreto },
url = {https://ui.adsabs.harvard.edu/abs/2024arXiv240619536G/abstract},
doi = {2406.19536},
year = {2024},
date = {2024-06-27},
journal = {ACSOmega},
pages = {15},
abstract = {Tetra-Penta-Deca-Hexa-graphene (TPDH) is a new 2D carbon allotrope with attractive electronic and mechanical properties. It is composed of tetragonal, pentagonal, and hexagonal carbon rings. When TPDH-graphene is sliced into quasi-one-dimensional (1D) structures like nanoribbons, it exhibits a range of behaviors, from semi-metallic to semiconducting. An alternative approach to achieving these desirable electronic (electronic confinement and/or non-zero electronic band gap) properties is the creation of nanotubes (TPDH-NT). In the present work, we carried out a comprehensive study of TPDH-NTs combining Density Functional Theory (DFT) and Classical Reactive Molecular Dynamics (MD). Our results show structural stability and a chiral dependence on mechanical properties. Similarly to standard carbon nanotubes, TPDH-NT can be metallic or semiconductor. MD results show Young's modulus values exceeding 700 GPa, except for nanotubes with very small radii. However, certain chiral TPDH-NTs (n,m) display values both below and above 700 GPa, particularly for those with small radii. The analyses of the angle and C-C bond length distributions underscore the significance of the tetragonal and pentagonal rings in determining the mechanical response of TPDH-NTs (n,0) and (0,n), respectively. },
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Tetra-Penta-Deca-Hexa-graphene (TPDH) is a new 2D carbon allotrope with attractive electronic and mechanical properties. It is composed of tetragonal, pentagonal, and hexagonal carbon rings. When TPDH-graphene is sliced into quasi-one-dimensional (1D) structures like nanoribbons, it exhibits a range of behaviors, from semi-metallic to semiconducting. An alternative approach to achieving these desirable electronic (electronic confinement and/or non-zero electronic band gap) properties is the creation of nanotubes (TPDH-NT). In the present work, we carried out a comprehensive study of TPDH-NTs combining Density Functional Theory (DFT) and Classical Reactive Molecular Dynamics (MD). Our results show structural stability and a chiral dependence on mechanical properties. Similarly to standard carbon nanotubes, TPDH-NT can be metallic or semiconductor. MD results show Young's modulus values exceeding 700 GPa, except for nanotubes with very small radii. However, certain chiral TPDH-NTs (n,m) display values both below and above 700 GPa, particularly for those with small radii. The analyses of the angle and C-C bond length distributions underscore the significance of the tetragonal and pentagonal rings in determining the mechanical response of TPDH-NTs (n,0) and (0,n), respectively.
Sengupta, Shilpi; Pramanik, Atin; de Oliveira, Caique Campos; Chattopadhyay, Shreyasi; Pieshkov, Tymofii; da Silva Autreto, Pedro Alves; Ajayan, Pulickel M; Kundu, Manab
Deciphering Sodium‐Ion Storage: 2D‐Sulfide versus Oxide Through Experimental and Computational Analyses Journal Article
Em: Small, vol. 20, iss. 38, 2024.
Resumo | Links | BibTeX | Tags:
@article{,
title = {Deciphering Sodium‐Ion Storage: 2D‐Sulfide versus Oxide Through Experimental and Computational Analyses},
author = {Shilpi Sengupta and Atin Pramanik and Caique Campos de Oliveira and Shreyasi Chattopadhyay and Tymofii Pieshkov and Pedro Alves da Silva Autreto and Pulickel M Ajayan and Manab Kundu},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/smll.202403321},
doi = {202403321},
year = {2024},
date = {2024-06-05},
urldate = {2024-06-05},
journal = {Small},
volume = {20},
issue = {38},
abstract = {Transition metal derivatives exhibit high theoretical capacity, making them promising anode materials for sodium-ion batteries. Sulfides, known for their superior electrical conductivity compared to oxides, enhance charge transfer, leading to improved electrochemical performance. Here, a hierarchical WS2 micro-flower is synthesized by thermal sulfurization of WO3. Comprising interconnected thin nanosheets, this structure offers increased surface area, facilitating extensive internal surfaces for electrochemical redox reactions. The WS2 micro-flower demonstrates a specific capacity of ≈334 mAh g−1 at 15 mA g−1, nearly three times higher than its oxide counterpart. Further, it shows very stable performance as a high-temperature (65 °C) anode with ≈180 mAh g−1 reversible capacity at 100 mA g−1 current rate. Post-cycling analysis confirms unchanged morphology, highlighting the structural stability and robustness of WS2. DFT calculations show that the electronic bandgap in both WS2 and WO3 increases when going from the bulk to monolayers. Na adsorption calculations show that Na atoms bind strongly in WO3 with a higher energy diffusion barrier when compared to WS2, corroborating the experimental findings. This study presents a significant insight into electrode material selection for sodium-ion storage applications.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Transition metal derivatives exhibit high theoretical capacity, making them promising anode materials for sodium-ion batteries. Sulfides, known for their superior electrical conductivity compared to oxides, enhance charge transfer, leading to improved electrochemical performance. Here, a hierarchical WS2 micro-flower is synthesized by thermal sulfurization of WO3. Comprising interconnected thin nanosheets, this structure offers increased surface area, facilitating extensive internal surfaces for electrochemical redox reactions. The WS2 micro-flower demonstrates a specific capacity of ≈334 mAh g−1 at 15 mA g−1, nearly three times higher than its oxide counterpart. Further, it shows very stable performance as a high-temperature (65 °C) anode with ≈180 mAh g−1 reversible capacity at 100 mA g−1 current rate. Post-cycling analysis confirms unchanged morphology, highlighting the structural stability and robustness of WS2. DFT calculations show that the electronic bandgap in both WS2 and WO3 increases when going from the bulk to monolayers. Na adsorption calculations show that Na atoms bind strongly in WO3 with a higher energy diffusion barrier when compared to WS2, corroborating the experimental findings. This study presents a significant insight into electrode material selection for sodium-ion storage applications.
de Oliveira, Caique Campos; Galvao, Douglas Soares; da Silva Autreto, Pedro Alves
Selective Hydrogenation Promotes the Anisotropic Thermoelectric Properties of TPDH-Graphene Journal Article
Em: The Journal of Physical Chemistry C, vol. 128, iss. 15, pp. 6206–6212, 2024.
Resumo | Links | BibTeX | Tags:
@article{nokey,
title = {Selective Hydrogenation Promotes the Anisotropic Thermoelectric Properties of TPDH-Graphene},
author = {Caique Campos de Oliveira and Douglas Soares Galvao and Pedro Alves da Silva Autreto},
url = {https://pubs.acs.org/doi/full/10.1021/acs.jpcc.4c00175},
doi = {4c00175},
year = {2024},
date = {2024-03-28},
journal = {The Journal of Physical Chemistry C},
volume = {128},
issue = {15},
pages = {6206–6212},
abstract = {We have combined density functional theory calculations with the Boltzmann semiclassical transport theory to investigate the effect of selective hydrogenation on the thermoelectric properties of tetra-penta-decahexagonal graphene (TPDH-gr), a recently proposed new two-dimensional carbon allotrope. Our results show that the Seebeck coefficient is enhanced after hydrogenation. The conductivity along the x direction is increased almost eight times while being almost suppressed along the y direction. This behavior can be understood in terms of the electronic structure changes due to the appearance of a Dirac-like cone after selective hydrogenation. Consistent with the literature, the electronic contribution to the thermal conductivity displays the same qualitative behavior as the conductivity, as expected from the Wiedemann–Franz law. The increase in thermal conductivity with temperature limits the material’s power factor. The significant increases in the Seebeck coefficient and conductivity also contribute to the thermal conductivity increase. These results show that hydrogenation is an effective method to improve the TPDH-gr thermoelectric properties, and this carbon allotrope can be an effective material for thermoelectric applications.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
We have combined density functional theory calculations with the Boltzmann semiclassical transport theory to investigate the effect of selective hydrogenation on the thermoelectric properties of tetra-penta-decahexagonal graphene (TPDH-gr), a recently proposed new two-dimensional carbon allotrope. Our results show that the Seebeck coefficient is enhanced after hydrogenation. The conductivity along the x direction is increased almost eight times while being almost suppressed along the y direction. This behavior can be understood in terms of the electronic structure changes due to the appearance of a Dirac-like cone after selective hydrogenation. Consistent with the literature, the electronic contribution to the thermal conductivity displays the same qualitative behavior as the conductivity, as expected from the Wiedemann–Franz law. The increase in thermal conductivity with temperature limits the material’s power factor. The significant increases in the Seebeck coefficient and conductivity also contribute to the thermal conductivity increase. These results show that hydrogenation is an effective method to improve the TPDH-gr thermoelectric properties, and this carbon allotrope can be an effective material for thermoelectric applications.
Khatun, Salma; Alanwoko, Onyedikachi; Pathirage, Vimukthi; de Oliveira, Caique Campos; Tromer, Raphael M.; da Silva Autreto, Pedro Alves; Galvao, Douglas Soares; Batzill, Matthias
Solid State Reaction Epitaxy, A New Approach for Synthesizing Van der Waals heterolayers: The Case of Mn and Cr on Bi2Se3 Journal Article
Em: Advance Functional Materials, vol. 34, iss. 28, 2024.
Resumo | Links | BibTeX | Tags:
@article{nokey,
title = {Solid State Reaction Epitaxy, A New Approach for Synthesizing Van der Waals heterolayers: The Case of Mn and Cr on Bi2Se3},
author = {Salma Khatun and Onyedikachi Alanwoko and Vimukthi Pathirage and Caique Campos de Oliveira and Raphael M. Tromer and Pedro Alves da Silva Autreto and Douglas Soares Galvao and Matthias Batzill},
url = {https://onlinelibrary.wiley.com/doi/full/10.1002/adfm.202315112},
doi = {202315112},
year = {2024},
date = {2024-03-12},
urldate = {2024-03-12},
journal = {Advance Functional Materials},
volume = {34},
issue = {28},
abstract = {Van der Waals (vdW) heterostructures that pair materials with diverse properties enable various quantum phenomena. However, the direct growth of vdW heterostructures is challenging. Modification of the surface layer of quantum materials to introduce new properties is an alternative process akin to solid state reaction. Here, vapor deposited transition metals (TMs), Cr and Mn, are reacted with Bi2Se3 with the goal to transform the surface layer to XBi2Se4 (X = Cr, Mn). Experiments and ab initio MD simulations demonstrate that the TMs have a high selenium affinity driving Se diffusion toward the TM. For monolayer Cr, the surface Bi2Se3 is reduced to Bi2-layer and a stable (pseudo) 2D Cr1+δSe2 layer is formed. In contrast, monolayer Mn can transform upon mild annealing into MnBi2Se4. This phase only forms for a precise amount of initial Mn deposition. Sub-monolayer amounts dissolve into the bulk, and multilayers form stable MnSe adlayers. This study highlights the delicate energy balance between adlayers and desired surface modified layers that governs the interface reactions and that the formation of stable adlayers can prevent the reaction with the substrate. The success of obtaining MnBi2Se4 points toward an approach for the engineering of other multicomponent vdW materials by surface reactions.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Van der Waals (vdW) heterostructures that pair materials with diverse properties enable various quantum phenomena. However, the direct growth of vdW heterostructures is challenging. Modification of the surface layer of quantum materials to introduce new properties is an alternative process akin to solid state reaction. Here, vapor deposited transition metals (TMs), Cr and Mn, are reacted with Bi2Se3 with the goal to transform the surface layer to XBi2Se4 (X = Cr, Mn). Experiments and ab initio MD simulations demonstrate that the TMs have a high selenium affinity driving Se diffusion toward the TM. For monolayer Cr, the surface Bi2Se3 is reduced to Bi2-layer and a stable (pseudo) 2D Cr1+δSe2 layer is formed. In contrast, monolayer Mn can transform upon mild annealing into MnBi2Se4. This phase only forms for a precise amount of initial Mn deposition. Sub-monolayer amounts dissolve into the bulk, and multilayers form stable MnSe adlayers. This study highlights the delicate energy balance between adlayers and desired surface modified layers that governs the interface reactions and that the formation of stable adlayers can prevent the reaction with the substrate. The success of obtaining MnBi2Se4 points toward an approach for the engineering of other multicomponent vdW materials by surface reactions.
Lucchetti, Lanna E. B.; da Silva Autreto, Pedro Alves; Santos, Mauro C.; de Almeida, James M.
Cerium doped graphene-based materials towards oxygen reduction reaction catalysis Journal Article
Em: Materials Today Communications, vol. 38, não 108461, 2024.
Resumo | Links | BibTeX | Tags:
@article{nokey,
title = {Cerium doped graphene-based materials towards oxygen reduction reaction catalysis},
author = {Lanna E.B. Lucchetti and Pedro Alves da Silva Autreto and Mauro C. Santos and James M. de Almeida},
url = {https://www.sciencedirect.com/science/article/pii/S2352492824004410},
doi = {2024.108461},
year = {2024},
date = {2024-02-23},
urldate = {2024-02-23},
journal = {Materials Today Communications},
volume = {38},
number = {108461},
abstract = {With the global transition towards cleaner energy and sustainable processes, the demand for efficient catalysts, especially for the oxygen reduction reaction, has gained attention from the scientific community. This research work investigates cerium-doped graphene-based materials as catalysts for this process with density functional theory calculations. The electrochemical performance of Ce-doped graphene was assessed within the computation hydrogen electrode framework. Our findings reveal that Ce doping, especially when synergized with an oxygen atom, shows improved catalytic activity and selectivity. For instance, Ce doping in combination with an oxygen atom, located near a border, can be selective for the 2-electron pathway. Overall, the combination of Ce doping with structural defects and oxygenated functions lowers the reaction free energies for the oxygen reduction compared to pure graphene, and consequently, might improve the catalytic activity. This research sheds light from a computational perspective on Ce-doped carbon materials as a sustainable alternative to traditional costly metal-based catalysts, offering promising prospects for green energy technologies and electrochemical applications.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
With the global transition towards cleaner energy and sustainable processes, the demand for efficient catalysts, especially for the oxygen reduction reaction, has gained attention from the scientific community. This research work investigates cerium-doped graphene-based materials as catalysts for this process with density functional theory calculations. The electrochemical performance of Ce-doped graphene was assessed within the computation hydrogen electrode framework. Our findings reveal that Ce doping, especially when synergized with an oxygen atom, shows improved catalytic activity and selectivity. For instance, Ce doping in combination with an oxygen atom, located near a border, can be selective for the 2-electron pathway. Overall, the combination of Ce doping with structural defects and oxygenated functions lowers the reaction free energies for the oxygen reduction compared to pure graphene, and consequently, might improve the catalytic activity. This research sheds light from a computational perspective on Ce-doped carbon materials as a sustainable alternative to traditional costly metal-based catalysts, offering promising prospects for green energy technologies and electrochemical applications.
Trench, Aline B.; Fernandes, Caio Machado; Moura, João Paulo C.; Lucchetti, Lanna E. B.; Lima, Thays S.; Antonin, Vanessa S.; de Almeida, James M.; da Silva Autreto, Pedro Alves; Robles, Irma; Motheo, Artur J.; Lanza, Marcos R. V.; Santos, Mauro C.
Hydrogen peroxide electrogeneration from O2 electroreduction: A review focusing on carbon electrocatalysts and environmental applications Journal Article
Em: Chemosphere, vol. 352, pp. 141456, 2024.
Resumo | Links | BibTeX | Tags:
@article{nokey,
title = {Hydrogen peroxide electrogeneration from O2 electroreduction: A review focusing on carbon electrocatalysts and environmental applications},
author = {Aline B. Trench and Caio Machado Fernandes and João Paulo C. Moura and Lanna E.B. Lucchetti and Thays S. Lima and Vanessa S. Antonin and James M. de Almeida and Pedro Alves da Silva Autreto and Irma Robles and Artur J. Motheo and Marcos R.V. Lanza and Mauro C. Santos },
url = {https://www.sciencedirect.com/science/article/pii/S0045653524003497},
doi = {2024.141456},
year = {2024},
date = {2024-02-15},
journal = {Chemosphere},
volume = {352},
pages = {141456},
abstract = {Hydrogen peroxide (H2O2) stands as one of the foremost utilized oxidizing agents in modern times. The established method for its production involves the intricate and costly anthraquinone process. However, a promising alternative pathway is the electrochemical hydrogen peroxide production, accomplished through the oxygen reduction reaction via a 2-electron pathway. This method not only simplifies the production process but also upholds environmental sustainability, especially when compared to the conventional anthraquinone method. In this review paper, recent works from the literature focusing on the 2-electron oxygen reduction reaction promoted by carbon electrocatalysts are summarized. The practical applications of these materials in the treatment of effluents contaminated with different pollutants (drugs, dyes, pesticides, and herbicides) are presented. Water treatment aiming to address these issues can be achieved through advanced oxidation electrochemical processes such as electro-Fenton, solar-electro-Fenton, and photo-electro-Fenton. These processes are discussed in detail in this work and the possible radicals that degrade the pollutants in each case are highlighted. The review broadens its scope to encompass contemporary computational simulations focused on the 2-electron oxygen reduction reaction, employing different models to describe carbon-based electrocatalysts. Finally, perspectives and future challenges in the area of carbon-based electrocatalysts for H2O2 electrogeneration are discussed. This review paper presents a forward-oriented viewpoint of present innovations and pragmatic implementations, delineating forthcoming challenges and prospects of this ever-evolving field.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Hydrogen peroxide (H2O2) stands as one of the foremost utilized oxidizing agents in modern times. The established method for its production involves the intricate and costly anthraquinone process. However, a promising alternative pathway is the electrochemical hydrogen peroxide production, accomplished through the oxygen reduction reaction via a 2-electron pathway. This method not only simplifies the production process but also upholds environmental sustainability, especially when compared to the conventional anthraquinone method. In this review paper, recent works from the literature focusing on the 2-electron oxygen reduction reaction promoted by carbon electrocatalysts are summarized. The practical applications of these materials in the treatment of effluents contaminated with different pollutants (drugs, dyes, pesticides, and herbicides) are presented. Water treatment aiming to address these issues can be achieved through advanced oxidation electrochemical processes such as electro-Fenton, solar-electro-Fenton, and photo-electro-Fenton. These processes are discussed in detail in this work and the possible radicals that degrade the pollutants in each case are highlighted. The review broadens its scope to encompass contemporary computational simulations focused on the 2-electron oxygen reduction reaction, employing different models to describe carbon-based electrocatalysts. Finally, perspectives and future challenges in the area of carbon-based electrocatalysts for H2O2 electrogeneration are discussed. This review paper presents a forward-oriented viewpoint of present innovations and pragmatic implementations, delineating forthcoming challenges and prospects of this ever-evolving field.
Moura, Alirio; Ipaves, Bruno; Galvao, Douglas Soares; da Silva Autreto, Pedro Alves
Ballistic properties of highly stretchable graphene kirigami pyramid Journal Article
Em: Computational Materials Science, vol. 232, 2024.
Resumo | Links | BibTeX | Tags:
@article{nokey,
title = {Ballistic properties of highly stretchable graphene kirigami pyramid},
author = {Alirio Moura and Bruno Ipaves and Douglas Soares Galvao and Pedro Alves da Silva Autreto},
url = {https://www.sciencedirect.com/science/article/abs/pii/S0927025623005529},
doi = {112558},
year = {2024},
date = {2024-01-25},
urldate = {2024-01-25},
journal = {Computational Materials Science},
volume = {232},
abstract = {Graphene kirigamis, characterized by patterned cuts, can enhance some of the graphene’s mechanical and electronic properties. In this work, we report the first study of the mechanical and ballistic behavior of single and multi- layered graphene kirigami pyramid (GKP). We have carried out fully atomistic reactive molecular dynamics simulations. The GKP structures exhibit a large kinetic energy absorption capability due to their topology, which creates multi-step dissipation mechanisms that block crack propagation. Our results demonstrate that even having significantly less mass, GKP can outperform graphene structures of similar dimensions in terms of absorbing kinetic energy capabilities.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Graphene kirigamis, characterized by patterned cuts, can enhance some of the graphene’s mechanical and electronic properties. In this work, we report the first study of the mechanical and ballistic behavior of single and multi- layered graphene kirigami pyramid (GKP). We have carried out fully atomistic reactive molecular dynamics simulations. The GKP structures exhibit a large kinetic energy absorption capability due to their topology, which creates multi-step dissipation mechanisms that block crack propagation. Our results demonstrate that even having significantly less mass, GKP can outperform graphene structures of similar dimensions in terms of absorbing kinetic energy capabilities.
2023
Mahapatra, Preeti Lata; de Oliveira, Caique Campos; Costin, Gelu; Sarkar, Suman; da Silva Autreto, Pedro Alves; Tiwary, Chandra Sekhar
Paramagnetic two-dimensional silicon-oxide from natural silicates Journal Article
Em: 2D Materials, vol. 11, 2023.
@article{,
title = {Paramagnetic two-dimensional silicon-oxide from natural silicates},
author = {Preeti Lata Mahapatra and Caique Campos de Oliveira and Gelu Costin and Suman Sarkar and Pedro Alves da Silva Autreto and Chandra Sekhar Tiwary},
url = {https://iopscience.iop.org/article/10.1088/2053-1583/ad10b9},
doi = {015019},
year = {2023},
date = {2023-12-12},
urldate = {2021-08-15},
journal = {2D Materials},
volume = {11},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Antonin, Vanessa S.; Lucchetti, Lanna E. B.; Souza, Felipe M.; Pinheiro, Victor S.; Moura, João Paulo C.; Trench, Aline B.; de Almeida, James M.; da Silva Autreto, Pedro Alves; Lanza, Marcos R. V.; Santos, Mauro C.
Sodium niobate microcubes decorated with ceria nanorods for hydrogen peroxide electrogeneration: An experimental and theoretical study Journal Article
Em: Journal of Alloys and Compounds, vol. 965, 2023.
Resumo | Links | BibTeX | Tags:
@article{,
title = {Sodium niobate microcubes decorated with ceria nanorods for hydrogen peroxide electrogeneration: An experimental and theoretical study},
author = {Vanessa S. Antonin and Lanna E.B. Lucchetti and Felipe M. Souza and Victor S. Pinheiro and João Paulo C. Moura and Aline B. Trench and James M. de Almeida and Pedro Alves da Silva Autreto and Marcos R.V. Lanza and Mauro C. Santos},
url = {https://www.sciencedirect.com/science/article/pii/S092583882302666X},
doi = {171363},
year = {2023},
date = {2023-11-25},
urldate = {2023-11-25},
journal = {Journal of Alloys and Compounds},
volume = {965},
abstract = {The present work investigates the catalytic activity of NaNbO3 microcubes decorated with CeO2 nanorods on carbon (1 %, 3 %, 5 %, and 10 % w/w) for H2O2 electrogeneration. The crystalline phases and the morphology of the materials were identified with scanning electron microscopy, transmission electron microscopy, X‐ray diffraction and X-ray Photoelectronic spectroscopy. Contact angle measurements were performed to characterize the hydrophilicity of each material. The H2O2 electrogeneration was assessed by oxygen reduction reaction using the rotating ring-disk electrode technique. Electrochemical characterization results shown an enhancement on the H2O2 electrogeneration by NaNbO3 @CeO2/C-based materials compared to what was obtained with pure Vulcan XC72. The 1 % NaNbO3 @CeO2/C electrocatalyst presented the lower starting potential for the ORR and a 2.3 electron transfer, favoring the 2-electron mechanism and providing a higher H2O2 electrogeneration rate. Also, the enhancement of oxygen-containing functional groups showed the potential to comprehensively tune properties and optimize active sites and, consequently, increases the H2O2 electrogeneration. Density functional theory calculations indicated that NaNbO3 and CeO2 surfaces have a similar low theoretical overpotential for this reaction and that CeO2 improves the catalyst facilitating the electron transfer. These results indicate that NaNbO3 @CeO2/C-based electrocatalysts are promising materials for in situ H2O2 electrogeneration.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The present work investigates the catalytic activity of NaNbO3 microcubes decorated with CeO2 nanorods on carbon (1 %, 3 %, 5 %, and 10 % w/w) for H2O2 electrogeneration. The crystalline phases and the morphology of the materials were identified with scanning electron microscopy, transmission electron microscopy, X‐ray diffraction and X-ray Photoelectronic spectroscopy. Contact angle measurements were performed to characterize the hydrophilicity of each material. The H2O2 electrogeneration was assessed by oxygen reduction reaction using the rotating ring-disk electrode technique. Electrochemical characterization results shown an enhancement on the H2O2 electrogeneration by NaNbO3 @CeO2/C-based materials compared to what was obtained with pure Vulcan XC72. The 1 % NaNbO3 @CeO2/C electrocatalyst presented the lower starting potential for the ORR and a 2.3 electron transfer, favoring the 2-electron mechanism and providing a higher H2O2 electrogeneration rate. Also, the enhancement of oxygen-containing functional groups showed the potential to comprehensively tune properties and optimize active sites and, consequently, increases the H2O2 electrogeneration. Density functional theory calculations indicated that NaNbO3 and CeO2 surfaces have a similar low theoretical overpotential for this reaction and that CeO2 improves the catalyst facilitating the electron transfer. These results indicate that NaNbO3 @CeO2/C-based electrocatalysts are promising materials for in situ H2O2 electrogeneration.
Mahapatra, Preeti Lata; de Oliveira, Caique Campos; Sreeram, P. R.; Sivaraman, Sivaraj Kanneth; Sarkar, Suman; Costin, Gelu; Lahiri, Basudev; da Silva Autreto, Pedro Alves; Tiwary, Chandra Sekhar
Hydrogen Sulfide Gas Detection Using Two-Dimensional Rhodonite Silicate Journal Article
Em: Chemistry of Materials, vol. 35, iss. 19, pp. 8135-8144, 2023.
Resumo | Links | BibTeX | Tags:
@article{nokey,
title = {Hydrogen Sulfide Gas Detection Using Two-Dimensional Rhodonite Silicate},
author = {Preeti Lata Mahapatra and Caique Campos de Oliveira and P. R. Sreeram and Sivaraj Kanneth Sivaraman and Suman Sarkar and Gelu Costin and Basudev Lahiri and Pedro Alves da Silva Autreto and Chandra Sekhar Tiwary},
url = {https://pubs.acs.org/doi/full/10.1021/acs.chemmater.3c01593},
doi = {3c01593},
year = {2023},
date = {2023-09-22},
journal = {Chemistry of Materials},
volume = {35},
issue = {19},
pages = {8135-8144},
abstract = {Hydrogen sulfide is a hazardous gas that is found in common industrial waste sources, including sewage and oil refineries; it is lethal at concentrations exceeding 100 ppm. Two-dimensional (2D) oxide materials with a high surface area and environmental stability can be utilized for ultralow concentration gas sensing (H2S gas). Here, we demonstrate the gas sensing properties of two-dimensional rhodonite silicate (R-silicate) extracted from natural mineral ore. 2D R-silicate shows high sensitivity of up to 0.2 ppm–1 and high selectivity toward H2S compared to CO2, ethanol, acetone, and ammonia. The sensors developed using 2D R-silicate are found to be stable after five months. The high surface area and composition consisting of Mn atoms play a significant role in the sensing behavior. Ab initio computing simulations explain the mechanism of the selectivity of H2S over CO2 using 2D R-silicate. The simulation also demonstrates the chemical interaction of H2S with the 2D surface of R-silicate, which is further supported by Raman spectroscopy. The findings of this study provide new opportunities for using environmentally stable natural silicate 2D materials as efficient replacements for conventional metal oxides for ultrasensitive sensors.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Hydrogen sulfide is a hazardous gas that is found in common industrial waste sources, including sewage and oil refineries; it is lethal at concentrations exceeding 100 ppm. Two-dimensional (2D) oxide materials with a high surface area and environmental stability can be utilized for ultralow concentration gas sensing (H2S gas). Here, we demonstrate the gas sensing properties of two-dimensional rhodonite silicate (R-silicate) extracted from natural mineral ore. 2D R-silicate shows high sensitivity of up to 0.2 ppm–1 and high selectivity toward H2S compared to CO2, ethanol, acetone, and ammonia. The sensors developed using 2D R-silicate are found to be stable after five months. The high surface area and composition consisting of Mn atoms play a significant role in the sensing behavior. Ab initio computing simulations explain the mechanism of the selectivity of H2S over CO2 using 2D R-silicate. The simulation also demonstrates the chemical interaction of H2S with the 2D surface of R-silicate, which is further supported by Raman spectroscopy. The findings of this study provide new opportunities for using environmentally stable natural silicate 2D materials as efficient replacements for conventional metal oxides for ultrasensitive sensors.
Buzelli, Thiago; Ipaves, Bruno; Almeida, Wanda Pereira; Galvao, Douglas Soares; da Silva Autreto, Pedro Alves
Machine Learning-based Analysis of Electronic Properties as Predictors of Anticholinesterase Activity in Chalcone Derivatives Working paper
2023.
Resumo | Links | BibTeX | Tags:
@workingpaper{nokey,
title = {Machine Learning-based Analysis of Electronic Properties as Predictors of Anticholinesterase Activity in Chalcone Derivatives},
author = {Thiago Buzelli and Bruno Ipaves and Wanda Pereira Almeida and Douglas Soares Galvao and Pedro Alves da Silva Autreto},
url = {https://arxiv.org/abs/2309.07312},
doi = {2309.07312},
year = {2023},
date = {2023-09-13},
journal = {Arxiv},
abstract = {In this study, we investigated the correlation between the electronic properties of anticholinesterase compounds and their biological activity. While the methodology of such correlation is well-established and has been effectively utilized in previous studies, we employed a more sophisticated approach: machine learning. Initially, we focused on a set of 22 molecules sharing a common chalcone skeleton and categorized them into two groups based on their IC50 indices: active and inactive. Utilizing the open-source software Orca, we conducted calculations to determine the geometries and electronic structures of these molecules. Over a hundred parameters were collected from these calculations, serving as the foundation for the features used in machine learning. These parameters included the Mulliken and Lowdin electronic populations of each atom within the skeleton, molecular orbital energies, and Mayer's free valences. Through our analysis, we developed numerous models and identified several successful candidates for effectively distinguishing between the two groups. Notably, the most informative descriptor for this separation relied solely on electronic populations and orbital energies. By understanding which computationally calculated properties are most relevant to specific biological activities, we can significantly enhance the efficiency of drug development processes, saving both time and resources.},
keywords = {},
pubstate = {published},
tppubtype = {workingpaper}
}
In this study, we investigated the correlation between the electronic properties of anticholinesterase compounds and their biological activity. While the methodology of such correlation is well-established and has been effectively utilized in previous studies, we employed a more sophisticated approach: machine learning. Initially, we focused on a set of 22 molecules sharing a common chalcone skeleton and categorized them into two groups based on their IC50 indices: active and inactive. Utilizing the open-source software Orca, we conducted calculations to determine the geometries and electronic structures of these molecules. Over a hundred parameters were collected from these calculations, serving as the foundation for the features used in machine learning. These parameters included the Mulliken and Lowdin electronic populations of each atom within the skeleton, molecular orbital energies, and Mayer's free valences. Through our analysis, we developed numerous models and identified several successful candidates for effectively distinguishing between the two groups. Notably, the most informative descriptor for this separation relied solely on electronic populations and orbital energies. By understanding which computationally calculated properties are most relevant to specific biological activities, we can significantly enhance the efficiency of drug development processes, saving both time and resources.
de Almeida, James M.; Machado, L D; Woellner, C F; Medina, Matheus; da Silva Autreto, Pedro Alves; Galvão, Douglas Soares
Boron nitride nanotube peapods at ultrasonic velocity impacts: a fully atomistic molecular dynamics investigation Journal Article
Em: Journal of Physics: Condensed Matter, vol. 35, 2023.
Resumo | Links | BibTeX | Tags:
@article{nokey,
title = {Boron nitride nanotube peapods at ultrasonic velocity impacts: a fully atomistic molecular dynamics investigation},
author = {James M. de Almeida and L D Machado and C F Woellner and Matheus Medina and Pedro Alves da Silva Autreto and Douglas Soares Galvão},
url = {https://iopscience.iop.org/article/10.1088/1361-648X/acd50b},
doi = {acd50b},
year = {2023},
date = {2023-05-23},
urldate = {2023-05-23},
journal = {Journal of Physics: Condensed Matter},
volume = {35},
abstract = {Boron nitride nanotube peapods (BNNT-peapod) are composed of linear chains of C60 molecules encapsulated inside BNNTs, they were first synthesized in 2003. In this work, we investigated the mechanical response and fracture dynamics of BNNT-peapods under ultrasonic velocity impacts (from 1 km s−1 up to 6 km s−1) against a solid target. We carried out fully atomistic reactive molecular dynamics simulations using a reactive force field. We have considered the case of horizontal and vertical shootings. Depending on the velocity values, we observed tube bending, tube fracture, and C60 ejection. Furthermore, the nanotube unzips for horizontal impacts at certain speeds, forming bi-layer nanoribbons 'incrusted' with C60 molecules. The methodology used here is applicable to other nanostructures. We hope it motivates other theoretical investigations on the behavior of nanostructures at ultrasonic velocity impacts and aid in interpreting future experimental results. It should be stressed that similar experiments and simulations were carried out on carbon nanotubes trying to obtain nanodiamonds. The present study expands these investigations to include BNNT.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Boron nitride nanotube peapods (BNNT-peapod) are composed of linear chains of C60 molecules encapsulated inside BNNTs, they were first synthesized in 2003. In this work, we investigated the mechanical response and fracture dynamics of BNNT-peapods under ultrasonic velocity impacts (from 1 km s−1 up to 6 km s−1) against a solid target. We carried out fully atomistic reactive molecular dynamics simulations using a reactive force field. We have considered the case of horizontal and vertical shootings. Depending on the velocity values, we observed tube bending, tube fracture, and C60 ejection. Furthermore, the nanotube unzips for horizontal impacts at certain speeds, forming bi-layer nanoribbons 'incrusted' with C60 molecules. The methodology used here is applicable to other nanostructures. We hope it motivates other theoretical investigations on the behavior of nanostructures at ultrasonic velocity impacts and aid in interpreting future experimental results. It should be stressed that similar experiments and simulations were carried out on carbon nanotubes trying to obtain nanodiamonds. The present study expands these investigations to include BNNT.
de Oliveira, Caique Campos; Medina, Matheus; Galvão, Douglas Soares; da Silva Autreto, Pedro Alves
Tetra-penta-deca-hexagonal-graphene (TPDH-graphene) hydrogenation patterns: dynamics and electronic structure Journal Article
Em: Physical Chemistry Chemical Physics, vol. 25, pp. 13088-13093, 2023.
Resumo | Links | BibTeX | Tags:
@article{nokey,
title = {Tetra-penta-deca-hexagonal-graphene (TPDH-graphene) hydrogenation patterns: dynamics and electronic structure},
author = {Caique Campos de Oliveira and Matheus Medina and Douglas Soares Galvão and Pedro Alves da Silva Autreto},
url = {https://pubs.rsc.org/en/content/articlelanding/2023/cp/d3cp00186e/},
doi = {D3CP00186E},
year = {2023},
date = {2023-04-13},
journal = {Physical Chemistry Chemical Physics},
volume = {25},
pages = {13088-13093},
abstract = {The advent of graphene has renewed the interest in other 2D carbon-based materials. In particular, new structures have been proposed by combining hexagonal and other carbon rings in different ways. Recently, Bhattacharya and Jana have proposed a new carbon allotrope, composed of different polygonal carbon rings containing 4, 5, 6, and 10 atoms, named tetra-penta-deca-hexagonal-graphene (TPDH-graphene). This unusual topology results in interesting mechanical, electronic, and optical properties with several potential applications, including UV protection. Like other 2D carbon structures, chemical functionalizations can be used to tune TPDH-graphene's physical/chemical properties. In this work, we investigate the hydrogenation dynamics of TPDH-graphene and its effects on its electronic structure, combining DFT and fully atomistic reactive molecular dynamics simulations. Our results show that H atoms are mainly incorporated on tetragonal ring sites (up to 80% at 300 K), leading to the appearance of well-delimited pentagonal carbon stripes. The electronic structure of the hydrogenated structures shows the formation of narrow bandgaps with the presence of Dirac cone-like structures, indicative of anisotropic transport properties.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The advent of graphene has renewed the interest in other 2D carbon-based materials. In particular, new structures have been proposed by combining hexagonal and other carbon rings in different ways. Recently, Bhattacharya and Jana have proposed a new carbon allotrope, composed of different polygonal carbon rings containing 4, 5, 6, and 10 atoms, named tetra-penta-deca-hexagonal-graphene (TPDH-graphene). This unusual topology results in interesting mechanical, electronic, and optical properties with several potential applications, including UV protection. Like other 2D carbon structures, chemical functionalizations can be used to tune TPDH-graphene's physical/chemical properties. In this work, we investigate the hydrogenation dynamics of TPDH-graphene and its effects on its electronic structure, combining DFT and fully atomistic reactive molecular dynamics simulations. Our results show that H atoms are mainly incorporated on tetragonal ring sites (up to 80% at 300 K), leading to the appearance of well-delimited pentagonal carbon stripes. The electronic structure of the hydrogenated structures shows the formation of narrow bandgaps with the presence of Dirac cone-like structures, indicative of anisotropic transport properties.
de Oliveira, Caique Campos; da Silva Autreto, Pedro Alves
Optimized 2D nanostructures for catalysis of hydrogen evolution reactions Journal Article
Em: MRS Advances, vol. 8, pp. 307-310, 2023.
Resumo | Links | BibTeX | Tags:
@article{nokey,
title = {Optimized 2D nanostructures for catalysis of hydrogen evolution reactions},
author = {Caique Campos de Oliveira and Pedro Alves da Silva Autreto},
url = {https://link.springer.com/article/10.1557/s43580-023-00549-7},
doi = {s43580-023-00549-7},
year = {2023},
date = {2023-03-27},
journal = {MRS Advances},
volume = {8},
pages = {307-310},
abstract = {Electrochemical water splitting can produce hydrogen without harmful emissions. However, the need for more cheap and efficient catalysts presents a significant bottleneck for this technology. With a diverse chemical composition and electronic properties, transition metal dichalcogenides have been extensively investigated for catalysing hydrogen evolution reactions. Major approaches to enhance these materials’ activity are based on increasing active site counting and enhancing their intrinsic activity, which can be achieved by doping. In this work, we performed ab initio calculations to investigate the catalytic activity of pristine and Pt-doped 1 T-TiSe2. Our results show that basal plane transition metal sites are meta-stable for adsorption, while chalcogen sites are most favourable. Furthermore, catalytic activity was enhanced after the Pt introduction, as indicated by the change in the ∆G towards zero. Nonetheless, Pt sites exhibited the best activity among the investigated sites.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Electrochemical water splitting can produce hydrogen without harmful emissions. However, the need for more cheap and efficient catalysts presents a significant bottleneck for this technology. With a diverse chemical composition and electronic properties, transition metal dichalcogenides have been extensively investigated for catalysing hydrogen evolution reactions. Major approaches to enhance these materials’ activity are based on increasing active site counting and enhancing their intrinsic activity, which can be achieved by doping. In this work, we performed ab initio calculations to investigate the catalytic activity of pristine and Pt-doped 1 T-TiSe2. Our results show that basal plane transition metal sites are meta-stable for adsorption, while chalcogen sites are most favourable. Furthermore, catalytic activity was enhanced after the Pt introduction, as indicated by the change in the ∆G towards zero. Nonetheless, Pt sites exhibited the best activity among the investigated sites.
Lucchetti, Lanna E. B.; da Silva Autreto, Pedro Alves; de Almeida, James M.; Santos, Mauro C.; Siahrostami, Samira
Unravelling catalytic activity trends in ceria surfaces toward the oxygen reduction and water oxidation reactions Journal Article
Em: Reaction Chemistry & Engineering, vol. 8, pp. 1285-1293, 2023.
Resumo | Links | BibTeX | Tags:
@article{nokey,
title = {Unravelling catalytic activity trends in ceria surfaces toward the oxygen reduction and water oxidation reactions},
author = {Lanna E.B. Lucchetti and Pedro Alves da Silva Autreto and James M. de Almeida and Mauro C. Santos and Samira Siahrostami},
url = {https://pubs.rsc.org/en/content/articlehtml/2023/re/d3re00027c},
doi = {D3RE00027C},
year = {2023},
date = {2023-03-03},
journal = {Reaction Chemistry & Engineering},
volume = {8},
pages = {1285-1293},
abstract = {Improved catalysts are critical for more environmentally friendly, and long-term oxygen electrochemical reactions. Computational catalysis can provide atomic level information that is critical for optimizing the next generation of electrocatalysts. It has been demonstrated that by varying the exposed planes, the catalytic performance of metallic oxides can be tuned. Herein, we investigate the role of CeO2 surface orientations (100), (110), (111), (221), and (331) in enhancing catalytic activity toward various oxygen electrochemical reactions ranging from 4- and 2-electron oxygen reduction reactions (ORR) to 4-, 2- and 1-electron water oxidation reactions (WOR) using density functional theory (DFT) calculations in conjunction with the computational hydrogen electrode. Our results indicate that the CeO2(100) facet is the most promising for 4-electron ORR, with a theoretical limiting potential of 0.52 V. We also show that the presence of oxygen vacancies can enhance the 4-electron ORR activity of the CeO2(110) and CeO2(111) surfaces. Besides, CeO2(100) is selective for the 4-electron WOR while CeO2(110) and CeO2(111) are selective for the 2-electron and 1-electron WOR, respectively. Oxygen vacancies shift all the above three facets towards the 4-electron WOR. This work sheds light on the role of different ceria facets in various oxygen electrochemical reactions which is critical for developing better catalysts.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Improved catalysts are critical for more environmentally friendly, and long-term oxygen electrochemical reactions. Computational catalysis can provide atomic level information that is critical for optimizing the next generation of electrocatalysts. It has been demonstrated that by varying the exposed planes, the catalytic performance of metallic oxides can be tuned. Herein, we investigate the role of CeO2 surface orientations (100), (110), (111), (221), and (331) in enhancing catalytic activity toward various oxygen electrochemical reactions ranging from 4- and 2-electron oxygen reduction reactions (ORR) to 4-, 2- and 1-electron water oxidation reactions (WOR) using density functional theory (DFT) calculations in conjunction with the computational hydrogen electrode. Our results indicate that the CeO2(100) facet is the most promising for 4-electron ORR, with a theoretical limiting potential of 0.52 V. We also show that the presence of oxygen vacancies can enhance the 4-electron ORR activity of the CeO2(110) and CeO2(111) surfaces. Besides, CeO2(100) is selective for the 4-electron WOR while CeO2(110) and CeO2(111) are selective for the 2-electron and 1-electron WOR, respectively. Oxygen vacancies shift all the above three facets towards the 4-electron WOR. This work sheds light on the role of different ceria facets in various oxygen electrochemical reactions which is critical for developing better catalysts.
