scholarly journals Understanding Graphene Response to Neutral and Charged Lead Species: Theory and Experiment

Materials ◽  
2018 ◽  
Vol 11 (10) ◽  
pp. 2059 ◽  
Author(s):  
Ivan Shtepliuk ◽  
Maria Santangelo ◽  
Mikhail Vagin ◽  
Ivan Ivanov ◽  
Volodymyr Khranovskyy ◽  
...  
Keyword(s):  
Density Functional ◽  
Electrical Characterization ◽  
Deep Understanding ◽  
Water Quality Monitoring ◽  
Epitaxial Graphene ◽  
Charge Transfer Complexes ◽  
Adsorption Mechanisms ◽  
Redox Peak ◽  
Holistic Understanding ◽  
Lead Species

Deep understanding of binding of toxic Lead (Pb) species on the surface of two-dimensional materials is a required prerequisite for the development of next-generation sensors that can provide fast and real-time detection of critically low concentrations. Here we report atomistic insights into the Lead behavior on epitaxial graphene (Gr) on silicon carbide substrates by thorough complementary study of voltammetry, electrical characterization, Raman spectroscopy, and Density Functional Theory (DFT). It is verified that the epitaxial graphene exhibits quasi-reversible anode reactions in aqueous solutions, providing a well-defined redox peak for Pb species and good linearity over a concentration range from 1 nM to 1 µM. The conductometric approach offers another way to investigate Lead adsorption, which is based on the formations of stable charge-transfer complexes affecting the p-type conductivity of epitaxial graphene. Our results suggest the adsorption ability of the epitaxial graphene towards divalent Lead ions is concentration-dependent and tends to saturate at higher concentrations. To elucidate the mechanisms responsible for Pb adsorption, we performed DFT calculations and estimated the solvent-mediated interaction between Lead species in different oxidative forms and graphene. Our results provide central information regarding the energetics and structure of Pb-graphene interacting complexes that underlay the adsorption mechanisms of neutral and divalent Lead species. Such a holistic understanding favors design and synthesis of new sensitive materials for water quality monitoring.

Tuning Transition Metal Carbides Activity by Surface Metal Alloying: Case Study on CO2 Capture and Activation

2018 ◽  
Author(s):  
Marti Lopez ◽  
Luke Broderick ◽  
John J Carey ◽  
Francesc Vines ◽  
Michael Nolan ◽  
...  
Keyword(s):  
Transition Metal ◽  
Co2 Capture ◽  
Density Functional ◽  
Deep Understanding ◽  
Metal Carbides ◽  
Transition Metal Carbides ◽  
Adsorption Sites ◽  
Surface Metal ◽  
A Minor

<div>CO2 is one of the main actors in the greenhouse effect and its removal from the atmosphere is becoming an urgent need. Thus, CO2 capture and storage (CCS) and CO2 capture and usage (CCU) technologies are intensively investigated as technologies to decrease the concentration</div><div>of atmospheric CO2. Both CCS and CCU require appropriate materials to adsorb/release and adsorb/activate CO2, respectively. Recently, it has been theoretically and experimentally shown that transition metal carbides (TMC) are able to capture, store, and activate CO2. To further improve the adsorption capacity of these materials, a deep understanding of the atomic level processes involved is essential. In the present work, we theoretically investigate the possible effects of surface metal doping of these TMCs by taking TiC as a textbook case and Cr, Hf, Mo, Nb, Ta, V, W, and Zr as dopants. Using periodic slab models with large</div><div>supercells and state-of-the-art density functional theory based calculations we show that CO2 adsorption is enhanced by doping with metals down a group but worsened along the d series. Adsorption sites, dispersion and coverage appear to play a minor, secondary constant effect. The dopant-induced adsorption enhancement is highly biased by the charge rearrangement at the surface. In all cases, CO2 activation is found but doping can shift the desorption temperature by up to 135 K.</div>

scholarly journals Study of the Molecule Adsorption Process during the Molecular Doping

Nanomaterials ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 1899
Author(s):  
Mattia Pizzone ◽  
Maria Grazia Grimaldi ◽  
Antonino La La Magna ◽  
Neda Rahmani ◽  
Silvia Scalese ◽  
...  
Keyword(s):  
Density Functional ◽  
Electrical Characterization ◽  
Molecular Surface ◽  
Doping Profile ◽  
Electrical Measurements ◽  
Self Assembled Monolayer ◽  
Depth Study ◽  
Molecular Doping ◽  
Dopant Atoms ◽  
Molecular Layers

Molecular Doping (MD) involves the deposition of molecules, containing the dopant atoms and dissolved in liquid solutions, over the surface of a semiconductor before the drive-in step. The control on the characteristics of the final doped samples resides on the in-depth study of the molecule behaviour once deposited. It is already known that the molecules form a self-assembled monolayer over the surface of the sample, but little is known about the role and behaviour of possible multiple layers that could be deposited on it after extended deposition times. In this work, we investigate the molecular surface coverage over time of diethyl-propyl phosphonate on silicon, by employing high-resolution morphological and electrical characterization, and examine the effects of the post-deposition surface treatments on it. We present these data together with density functional theory simulations of the molecules–substrate system and electrical measurements of the doped samples. The results allow us to recognise a difference in the bonding types involved in the formation of the molecular layers and how these influence the final doping profile of the samples. This will improve the control on the electrical properties of MD-based devices, allowing for a finer tuning of their performance.

Electrical Characterization of the Graphene-SiC Heterojunction

2012 ◽  
Vol 717-720 ◽  
pp. 641-644
Author(s):  
Travis J. Anderson ◽  
Karl D. Hobart ◽  
Luke O. Nyakiti ◽  
Virginia D. Wheeler ◽  
Rachael L. Myers-Ward ◽  
...  
Keyword(s):  
Electrical Properties ◽  
Charge Carrier ◽  
Graphene Sheet ◽  
Carrier Transport ◽  
Electrical Characterization ◽  
Epitaxial Graphene ◽  
Charge Carrier Transport ◽  
Semiconductor System ◽  
Significant Research

Graphene, a 2D material, has motivated significant research in the study of its in-plane charge carrier transport in order to understand and exploit its unique physical and electrical properties. The vertical graphene-semiconductor system, however, also presents opportunities for unique devices, yet there have been few attempts to understand the properties of carrier transport through the graphene sheet into an underlying substrate. In this work, we investigate the epitaxial graphene/4H-SiC system, studying both p and n-type SiC substrates with varying doping levels in order to better understand this vertical heterojunction.

First-Principles Study of Interaction of Lithium Atoms with (3, 3) Carbon Nanotubes

2014 ◽  
Vol 687-691 ◽  
pp. 4311-4314 ◽  
Author(s):  
Shun Fu Xu ◽  
Ling Min Li
Keyword(s):  
Carbon Nanotubes ◽  
First Principles ◽  
Density Functional ◽  
Vacancy Defect ◽  
Single Wall Carbon Nanotubes ◽  
Generalized Gradient ◽  
Hydrogen Atoms ◽  
Functional Theory ◽  
Vacancy Defects ◽  
Adsorption Mechanisms

In this paper, we have employed first-principles calculations to investigate the adsorption mechanisms of one lithium atom on the sidewalls of 1/2/3 H-adsorbed indefective/defective (3, 3) single-wall carbon nanotubes (CNTs) which have vacancy defects. Our calculations are performed within density functional theory (DFT) under the generalized gradient approximation (GGA) of Perdew, Burke, and Ernzerhof (PBE).Our results show that the lithium atoms strongly binds to the H-adsorbed (3, 3) nanotube. Lithium atoms can chemically adsorb on (3, 3) nanotube with the vacancy defect (MVD) without any energy barrier. The lithium adsorption will enhance the electrical conductivity of the nanotube. Further more, the structure of the (3, 3) nanotube with the MVD and hydrogen atoms will become more stable after the three kinds of lithium adsorption.

scholarly journals Epitaxial Graphene Sensors Combined with 3D-Printed Microfluidic Chip for Heavy Metals Detection

Sensors ◽  
2019 ◽  
Vol 19 (10) ◽  
pp. 2393 ◽  
Author(s):  
Maria Francesca Santangelo ◽  
Ivan Shtepliuk ◽  
Daniel Filippini ◽  
Donatella Puglisi ◽  
Mikhail Vagin ◽  
...  
Keyword(s):  
Heavy Metals ◽  
Density Functional ◽  
Topological Analysis ◽  
Decomposition Analysis ◽  
Epitaxial Graphene ◽  
Phase Detection ◽  
Lab On Chip ◽  
Covalent Interaction ◽  
3D Printed ◽  
On Chip

In this work, we investigated the sensing performance of epitaxial graphene on Si-face 4H-SiC (EG/SiC) for liquid-phase detection of heavy metals (e.g., Pb and Cd), showing fast and stable response and low detection limit. The sensing platform proposed includes 3D-printed microfluidic devices, which incorporate all features required to connect and execute lab-on-chip (LOC) functions. The obtained results indicate that EG exhibits excellent sensing activity towards Pb and Cd ions. Several concentrations of Pb2+ solutions, ranging from 125 nM to 500 µM, were analyzed showing Langmuir correlation between signal and Pb2+ concentrations, good stability, and reproducibility over time. Upon the simultaneous presence of both metals, sensor response is dominated by Pb2+ rather than Cd2+ ions. To explain the sensing mechanisms and difference in adsorption behavior of Pb2+ and Cd2+ ions on EG in water-based solutions, we performed van-der-Waals (vdW)-corrected density functional theory (DFT) calculations and non-covalent interaction (NCI) analysis, extended charge decomposition analysis (ECDA), and topological analysis. We demonstrated that Pb2+ and Cd2+ ions act as electron-acceptors, enhancing hole conductivity of EG, due to charge transfer from graphene to metal ions, and Pb2+ ions have preferential ability to binding with graphene over cadmium. Electrochemical measurements confirmed the conductometric results, which additionally indicate that EG is more sensitive to lead than to cadmium.

Charge transfer complexes between 2-, 3- and 4-aminopyridines and some π-acceptors in the gas phase and in chloroform: DFT calculations

2016 ◽  
Vol 15 (04) ◽  
pp. 1650029 ◽  
Author(s):  
Nuha Ahmed Wazzan
Keyword(s):  
Charge Transfer ◽  
Dft Calculations ◽  
Gas Phase ◽  
Density Functional ◽  
Molecular Structures ◽  
Basis Set ◽  
Charge Transfer Complexes ◽  
Good Correspondence ◽  
Electronic Distribution ◽  
Picryl Chloride

This work reports density functional theory (DFT) calculations on the molecular structures, electronic distribution, and UV-Vis and IR spectroscopy analysis of charge transfer complexes between aminopyridines (APYs), namely 2-APY, 3-APY and 4-APY, as electron-donors and some [Formula: see text]-electron-acceptors, namely chloranil (CHL), tetracyanoethylene (TCNE) and picryl chloride (PC), formed in the gas phase at the B3LYP/6-31[Formula: see text]G(d,p) method/basis set, and in chloroform at the same method/basis set using PCM as solvation model. Good correspondence was generally obtained between the calculated parameters and the experimental ones.

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