Revision of the oxygen reduction reaction on N-doped graphenes by grand-canonical DFT.

Nitrogen-doped graphenes were among the first promising metal-free carbon-based catalysts for the oxygen reduction reaction (ORR). However, data on the most efficient catalytic centers and their catalytic mechanisms are still under debate. In this work, we study the associative mechanism of the ORR in an alkaline medium on graphene containing various types of nitrogen doping. The free energy profile of the reaction is constructed using grand-canonical DFT at a constant electrode potential in combination with an implicit electrolyte model. It is shown that the reaction mechanism differs from the generally accepted one and depends on the surface potential and doping type. In particular, as the potential decreases, coupled electron-proton transfer changes to sequential electron and proton transfer, and the potential at which this occurs depends on the doping type. It has been shown that oxygen chemisorption is the limiting step. The electrocatalytic mechanism of the nitrogen dopants involves reducing the oxygen chemisorption energy. Calculations predict that, at different potentials, different types of nitrogen impurities most effectively catalyze the ORR.

Toward On-Chip Multisensor Arrays for Selective Methanol and Ethanol Detection at Room Temperature: Capitalizing the Graphene Carbonylation.

The artificial olfaction units (or e-noses) capable of room-temperature operation are highly demanded to meet the requests of society in numerous vital applications and developing Internet-of-Things. Derivatized 2D crystals are considered as sensing elements of choice in this regard, unlocking the potential of the advanced e-nose technologies limited by the current semiconductor technologies. Herein, we consider fabrication and gas-sensing properties of On-chip multisensor arrays based on a hole-matrixed carbonylated (C-ny) graphene film with a gradually changed thickness and concentration of ketone groups of up to 12.5 at.%. The enhanced chemiresistive response of C-ny graphene toward methanol and ethanol, of hundred ppm concentration when mixing with air to match permissible exposure OSHA limits, at room-temperature operation is signified. Following thorough characterization via core-level techniques and density functional theory, the predominant role of the C-ny graphene-perforated structure and abundance of ketone groups in advancing the chemiresistive effect is established. Advancing practice applications, selective discrimination of the studied alcohols is approached by linear discriminant analysis employing a multisensor array's vector signal, and the fabricated chip's long-term performance is shown.

Correction: Modulation of the kinetics of outer-sphere electron transfer at graphene by a metal substrate.

Correction for 'Modulation of the kinetics of outer-sphere electron transfer at graphene by a metal substrate' by Sergey V. Pavlov et al., Phys. Chem. Chem. Phys., 2022, 24, 25203-25213, https://doi.org/10.1039/D2CP03771H.

Modulation of the kinetics of outer-sphere electron transfer at graphene by a metal substrate.

Solid-supported graphene is a typical configuration of electrochemical devices based on single-layer graphene. Therefore, it is necessary to understand the electrochemical features of such heterostructures. In this work, we theoretically investigated the effect of the metal type on the nonadiabatic electron transfer (ET) at the metal-supported graphene using DFT calculations. We considered five metals Au, Ag, Pt, Cu, and Al on which graphene is physically adsorbed. It is shown that all metals catalyze the ET. The electrocatalytic effect increases in the following series Al < Au ≲ Ag ≈ Cu < Pt. The enhanced ET in the presence of the metal substrate is explained by the hybridization of metal and graphene states, due to which the coupling between the reactant in an electrolyte and metal is increased. Metal-dependent electrocatalytic effect is explained both by different densities of states at the Fermi level of the systems and by differences in the behaviour of the tails of hybridized wave functions in the electrolyte region. The shift of the Fermi level with respect to the Dirac point in graphene when charging at the metal/graphene/electrolyte interface does not affect the kinetics due to the small contribution of graphene states to the electron transfer.

Manifesting Epoxide and Hydroxyl Groups in XPS Spectra and Valence Band of Graphene Derivatives.

The derivatization of graphene to engineer its band structure is a subject of significant attention nowadays, extending the frames of graphene material applications in the fields of catalysis, sensing, and energy harvesting. Yet, the accurate identification of a certain group and its effect on graphene's electronic structure is an intricate question. Herein, we propose the advanced fingerprinting of the epoxide and hydroxyl groups on the graphene layers via core-level methods and reveal the modification of their valence band (VB) upon the introduction of these oxygen functionalities. The distinctive contribution of epoxide and hydroxyl groups to the C 1s X-ray photoelectron spectra was indicated experimentally, allowing the quantitative characterization of each group, not just their sum. The appearance of a set of localized states in graphene's VB related to the molecular orbitals of the introduced functionalities was signified both experimentally and theoretically. Applying the density functional theory calculations, the impact of the localized states corresponding to the molecular orbitals of the hydroxyl and epoxide groups was decomposed. Altogether, these findings unveiled the particular contribution of the epoxide and hydroxyl groups to the core-level spectra and band structure of graphene derivatives, advancing graphene functionalization as a tool to engineer its physical properties.

Valence Band Structure Engineering in Graphene Derivatives.

Engineering of the 2D materials' electronic structure is at the forefront of nanomaterials research nowadays, giving an advance in the development of next-generation photonic devices, e-sensing technologies, and smart materials. Herein, employing core-level spectroscopy methods combined with density functional theory (DFT) modeling, the modification of the graphenes' valence band (VB) upon its derivatization by carboxyls and ketones is revealed. The appearance of a set of localized states in the VB of graphene related to molecular orbitals of the introduced functionalities is signified both experimentally and theoretically. Applying the DFT calculations of the density of states projected on the functional groups, their contributions to the VB structure are decomposed. An empirical approach, allowing one to analyze and predict the impact of a certain functional group on the graphenes' electronic structure in terms of examination of the model molecules, mimicking the introduced functionality, is proposed and validated. The interpretation of the arising states origin is made and their designation, pointing out their symmetry type, is proposed. Taken together, these results guide the band structure engineering of graphene derivatives and give a hint on the mechanisms underlying the alteration of the VB structure of 2D materials upon their derivatization.

Effect of a Au underlayer on outer-sphere electron transfer across a Au/graphene/electrolyte interface.

The effect of a gold underlayer on the outer-sphere non-adiabatic electron transfer on a graphene surface is investigated theoretically using both periodic and cluster DFT calculations. We propose a model that describes the alignment of energy levels and charge redistribution at the metal/graphene/redox electrolyte interface. Model calculations were performed for the [Fe(CN)6]3-/4- and [Ru(NH3)6]3+/2+ redox couples. It is shown that the gold support increases the rate constant of electron transfer. Gold electronic states hybridize with graphene wave functions, which provides an effective overlap with reactant orbitals outside the graphene layer and favors an increasing reaction rate. Although the Fermi level shift relative to the Dirac point in graphene depends significantly on the redox couple, this weakly affects the electron transfer kinetics at the Au(111)/graphene/electrolyte interface due to a small contribution of graphene states to the rate constant as compared to gold ones.

Trait anxiety impact on posterior activation asymmetries at rest and during evoked negative emotions: EEG investigation.

The main objective of the present investigation was to examine how high trait anxiety would influence cortical EEG asymmetries under non-emotional conditions and while experiencing negative emotions. The 62-channel EEG was recorded in control (n=21) and high anxiety (HA, n=18) non-patient individuals. Results showed that in HA subjects, the lowest level of arousal (eyes closed) was associated with stronger right-sided parieto-temporal theta-1 (4-6 Hz) and beta-1 (12-18 Hz) activity, whereas increased non-emotional arousal (eyes open, viewing neutral movie clip) was marked by persisting favored right hemisphere beta-1 activity. In turn, viewing aversive movie clip by the HA group led to significant lateralized decrease of the right parieto-temporal beta-1 power, which was initially higher in the emotionally neutral conditions. The EEG data suggests that asymmetrical parieto-temporal theta-1 and beta-1 EEG activity might be better interpreted in terms of Gray's BAS and BIS theory.

Trait anxiety impact on the EEG theta band power changes during appraisal of threatening and pleasant visual stimuli.

The main objective of the present investigation was to examine whether trait anxiety construct would influence EEG event-related synchronization (ERS) of the theta power during viewing of visual threatening stimuli. The 62-channel EEG was recorded while low (LA, n= 18) and high (HA, n= 18) trait-anxious subjects viewed sequentially presented neutral, threatening and pleasant pictures. Between-group differences, related to stimulus emotionality, were linked to the test period of 0-1000 ms after stimulus onset. In the low theta (4-6 Hz) at prefrontal sites HA exhibited deficient ERS in response to both threatening and pleasant stimuli in the right hemisphere, whereas LA yielded larger right than left hemisphere ERS in response to all the three stimulus categories. In the upper theta (6-8 Hz) group differences were associated with posterior cortical regions: HA exhibited the largest ERS to threatening and the lowest to pleasant stimuli, whereas LA prompted the largest ERS to pleasant and the lowest to neutral pictures. It is suggested that low theta right prefrontal hypoactivation favoring left hemispheric (i.e. more analytical) activity along with higher upper theta ERS of posterior cortical regions (i.e. enhanced higher order visual processing) to threatening stimuli could form the basis for neuropsychologically observed general bias towards threatening information in HA.

Time-dependent cortical asymmetries induced by emotional arousal: EEG analysis of event-related synchronization and desynchronization in individually defined frequency bands.

Event-related desynchronization (ERD) and synchronization (ERS) in the individually defined theta, alpha-1, alpha-2 and alpha-3 frequency bands were measured in 20 healthy subjects in response to International Affective Picture System (IAPS) stimuli with low, moderate and high arousal (LA, MA and HA) content. The 62-channel EEG, skin conductance response (SCR) and heart rate (HR) were simultaneously recorded while subjects viewed sequentially presented pictures and subjectively rated them after each presentation. In the theta band, both MA and HA vs. LA stimuli induced larger synchronization over the left anterior and bilaterally over posterior cortical leads. However, rather unexpectedly, both MA and HA vs. LA stimuli yielded larger alpha-1 synchronization, predominantly over occipital leads. In both theta and alpha-1 bands, affectively salient stimuli prompted larger ERS against the background of the overall dominance in power synchronization of posterior regions of the right hemisphere, irrespective of stimulus category. Finally, in the alpha-3 band, HA stimuli induce a lateralized time-dependent power increase over anterior leads of the left hemisphere. The hemispheric asymmetries revealed point to recruitment of not only posterior regions of the right hemisphere (theta and alpha-1 bands), but also of anterior regions of the left hemisphere (theta and alpha-3 bands) in affect analysis beyond valence dimension. In terms of affective chronometry, the significant arousalxtime interactions clearly indicate that in the theta frequency band discrimination of affective stimuli has already started at 200 ms post-stimulus, whereas in the alpha-1 and alpha-3 bands this process is delayed by up to 800-1200 ms.