31 research outputs found
Study of Alkylthiolate Self-Assembled Monolayers on Au(111) using a Semilocal meta-GGA Density Functional
We present a density functional theory study of the structure and stability of self-assembled monolayers (SAMs) of alkylthiolate on Au(111) as a function of the alkyl chain length. The most favorable structure of the SAMs involves an RSâAuâSR complex (S being sulfur, R being an alkyl chain) formed through sandwiching one Au adatom by two alkylthiolates (RSs). Comparing a generalized gradient (GGA-PBE) and a meta-GGA (MGGA-M06-L) exchange-correlation functional we find that only the meta-GGA functional predicts the experimentally observed attractive intermolecular interactions within the SAMs. In particular, the use of M06-L yields an increased stability of the SAMs with increasing alkyl chain length and an increased attractive interaction between RSâAuâSR complexes at shorter distances
Boosting Graphene Reactivity with Oxygen by Boron Doping: Density Functional Theory Modeling of the Reaction Path.
Graphene
(G) reactivity toward oxygen is very poor, which limits
its use as electrode for the oxygen reduction reaction (ORR). Contrarily,
boron-doped graphene was found to be an excellent catalyst for the
ORR. Through a density functional study, comparing molecular and periodic
approaches and different functionals (B3LYP vs PBE), we show how substitutional
boron in the carbon sheet can boost the reactivity with oxygen leading
to the formation of bulk borates covalently bound to graphene (BO<sub>3</sub>âG) in oxygen-rich conditions. These species are highly
interesting intermediates for the OîťO breaking step in the
reduction process of O<sub>2</sub> to form H<sub>2</sub>O as they
are energetically stable
Keeping track of samples in multidisciplinary fieldwork
We here present methods, tools and results for efficiently collecting metadata and
tracking samples collected in the field. The samples and metadata were collected during
scientific cruises conducted by amongst others marine biologists, oceanographers,
geochemists and marine geologists in the Nansen Legacy project. It is here reported on
the successful development and implementation of a system for labeling, tracking and
openly publishing metadata from the cruises. The results and tools have been made
openly available, as they are suitable for a range of situations, from the individual
scientist working in the field to large research missions
Treatment of Layered Structures Using a Semilocal meta-GGA Density Functional
Density functional theory calculations on solids consisting of covalently bonded layers held together by dispersive interactions are presented. Utilizing the kinetic energy density in addition to the density and its gradients gives the meta-generalized gradient approximation (MGGA) M06-L enough flexibility to treat correctly both the covalent and the dispersive interactions in layered solids, thus making it a significant step forward compared to the local density and generalized gradient approximations. We show how the MGGA can take advantage of the extra information in the kinetic energy density to discriminate between dispersive and covalent interactions and thereby prove that the performance of M06-L for dispersive interactions, as opposed to that for the local density approximation, is not based on an accidental cancellation of errors
Catalysis under Cover: Enhanced Reactivity at the Interface between (Doped) Graphene and Anatase TiO<sub>2</sub>
The âcatalysis
under coverâ involves chemical processes
which take place in the confined zone between a 2D material, such
as graphene, h-BN, or MoS<sub>2</sub>, and the surface of an underlying
support, such as a metal or a semiconducting oxide. The hybrid interface
between graphene and anatase TiO<sub>2</sub> is extremely important
for photocatalytic and catalytic applications because of the excellent
and complementary properties of the two materials. We investigate
and discuss the reactivity of O<sub>2</sub> and H<sub>2</sub>O on
top and at the interface of this hybrid system by means of a wide
set of dispersion-corrected hybrid density functional calculations.
Both pure and boron- or nitrogen-doped graphene are interfaced with
the most stable (101) anatase surface of TiO<sub>2</sub> in order
to improve the chemical activity of the C-layer. Especially in the
case of boron, an enhanced reactivity toward O<sub>2</sub> dissociation
is observed as a result of both the contribution of the dopant and
of the confinement effect in the bidimensional area between the two
surfaces. Extremely stable dissociation products are observed where
the boron atom bridges the two systems by forming very stable Bî¸O
covalent bonds. Interestingly, the B defect in graphene could also
act as the transfer channel of oxygen atoms from the top side across
the C atomic layer into the G/TiO<sub>2</sub> interface. On the contrary,
the same conditions are not found to favor water dissociation, proving
that the âcatalysis under coverâ is not a general effect,
but rather highly depends on the interfacing material properties,
on the presence of defects and impurities and on the specific reaction
involved
Water at the Interface Between Defective Graphene and Cu or Pt (111) Surfaces
The
presence of defects in the graphenic layers deposited on metal surfaces
modifies the nature of the interaction. Unsaturated carbon atoms,
due to vacancies in the lattice, form strong organometallic bonds
with surface metal atoms that highly enhance the binding energy between
the two materials. We investigate by means of a wide set of dispersion-corrected
density functional theory calculations how such strong chemical bonds
affect both the electronic properties of these hybrid interfaces and
the chemical reactivity with water, which is commonly present in the
working conditions. We compare different metal substrates (Cu vs Pt)
that present a different type of interaction with graphene and with
defective graphene. This comparative analysis allows us to unravel
the controlling factors of water reactivity, the role played by the
carbon vacancies and by the confinement or âgraphene cover
effectâ. Water is capable of breaking the CâCu bond
by dissociating at the undercoordinated carbon atom of the vacancy,
restoring the weak van der Waals type of interaction between the two
materials that allows for an easy detachment of graphene from the
metal, but the same is not true in the case of Pt, where CâPt
bonds are much stronger. These conclusions can be used to rationalize
water reactivity at other defective graphene/metal interfaces
Advances in operational permafrost monitoring on Svalbard and in Norway
The cryosphere web portal maintained by the Norwegian Meteorological Institute (MET Norway), https://cryo.met.no , provides access to the latest operational data and the current state of sea ice, snow, and permafrost in Norway, the Arctic, and the Antarctic. We present the latest addition to this portal: the operational permafrost monitoring at MET Norway and methods for visualising real-time permafrost temperature data. The latest permafrost temperatures are compared to the climatology generated from the stationâs data record, including median, confidence intervals, extremes, and trends. There are additional operational weather stations with extended measurement programs at these locations. The collocated monitoring offers daily updated data for studying and monitoring the current state, trends, and the effects of, e.g. extreme climate events on permafrost temperatures. Ground temperature rates obtained from the long-term records in the warmer permafrost found in Norway are typically 0.1 ^â Câ0.2 ^â C per decade. In contrast, in the colder permafrost of the High Arctic on Svalbard, a warming of up to 0.7 ^â C per decade is apparent. The operational monitoring provides information faster than ever before, potentially assisting in the early detection of, e.g. record high active layer thickness and pronounced permafrost temperature increases. It may also become an important cornerstone of early warning systems for natural hazards associated with permafrost warming and degradation. Currently, data are submitted manually to the international Global Terrestrial Network for Permafrost and are scheduled for integration with World Meteorological Organisation (WMO) operational services through the WMO Global Cryosphere Watch