Spray Deposition Synthesis of Locally Ordered Mesoporous Polycrystalline Titania Films at Low Temperature

A low-temperature spray deposition synthesis was developed to prepare locally hexagonally ordered mesoporous titania films with polycrystalline anatase pore walls in an evaporation-induced self-assembly process. The titania film preparation procedure is conducted completely at temperatures below 50◦C. The effects of spray time, film thickness, synthesis time prior to spray deposition, and aging time at high relative humidity after deposition on the atomic arrangement and the mesoorder of the mesoporous titania were studied. We find the crystallite size to depend on both the synthesis time and aging time of the films, where longer times result in larger crystallites. Using the photocatalytic activity of titania, the structure-directing agent is removed with UV radiation at 43–46◦C. The capability of the prepared films to remove the polymer template increased with longer synthesis and aging times due to the increased crystallinity, which increases the photocatalytic efficiency of the titania films. However, with increasingly longer times, the crystallites grow too large for the mesoorder of the pores to be maintained. This work shows that a scalable spray coating method can be used to prepare locally ordered mesoporous polycrystalline titania films by judiciously tuning the synthesis parameters

Electrochemical and structural characterization of lithiation in spray deposited ordered mesoporous titania as an anode for Li ion batteries

Ordered mesoporous titania, preparedvialow-temperature spray deposition, was examined as an anode material for lithium ion batteries. The material exhibits an exceptionally high electrochemical capacity of 680 mA h g-1during the first discharge, which rapidly decreases over the following cycles. The capacity stabilizes at around 170 mA h g-1after 50 cycles and the material delivers 83 mA h g-1at high charge/discharge rates (10C). A combination of electrochemical and structural characterization techniques were used to study the charge/discharge behavior of the material and the origin of the irreversible capacity. To determine the effect of cycling on the structure of the material, X-ray absorption spectroscopy (XAS) and energy filtered TEM were carried out on pristine and cycled samples in intercalated and deintercalated states. Titanium K-edge XAS measurements showed that intercalated lithium affects the NEXAFS region. By comparing peak intensity ratios, we propose a method to quantify the amount of lithium inserted into the titania structure and to differentiate between lithium bound in close proximity to titanium, and lithium bound further away from titanium. Additionally, we suggest that the irreversible loss in capacity is due to the formation of phases that are stable, and thereby electrochemically inactive, over the electrochemical cycling conditions applied

An imidazolium ionic liquid as effective structure-directing agent for the fabrication of silica thin films with vertically aligned nanochannels

In parallel to the increasing variety of ionic liquids that show different kinds of nanometer-scale structuration in their pure and solved forms, there is a raising interest in exploring the possibility of using ionic liquids as soft-templates for the synthesis of mesoporous materials. We report the case of 1-hexadecyl-3-methylimidazolium chloride (C16MIMCl), a surface active ionic liquid (SAIL), here used as an excellent soft-template for the formation of vertically aligned, uniform mesochannels, with a well defined pore width of 2.5 nm in silica thin films deposited with the electrochemically assisted self-assembly (EASA) method. The obtained mesochannels run through the entire thickness of the films and after removal of the ionic liquid the emptied mesochannels ensure a thorough mass transport to the substrate, here monitored by the redox-active electrochemical probe Ru(II)/Ru(III) during cyclic voltammetry (CV). Moreover, the mechanism of pore formation is explained; unlike the mechanisms reported for short chain imidazolium ionic liquid silica templates, in the case of C16MIMCl the dominating so-called cooperative interaction is the electrostatic attraction between the C16MIM+ and the network-forming negatively charged silicate oligomers. Therefore, this study provides a better understanding of the templating behavior of long chain imidazolium ionic liquids and motivates further research on the synthesis of ionic liquid-based functional hybrid materials

Impacts of Hydro-Climatically Varying Years on Ice Growth and Decay in a Subarctic River

Predicting the future changes in river ice development and impacts on seasonal sediment transport requires more in-depth examination of present river ice cover growth processes. This paper therefore investigates: (1) the impacts of hydro-climatically varying years on river ice development in a Scandinavian subarctic meandering river and (2) the accuracy of existing analytical models for predicting ice thickness growth and ice decay. Stefan's ice growth equation (version by Michel et al.) and Bilello's ice decay equation are applied to varying hydro-climatic conditions experienced in the years 2013-2019. Estimates from these equations are compared with observed field conditions such as ice thicknesses, ice clearance dates and freeze-thaw days. Overall, the equations were most accurate in the winter of 2016-2017 when the maximum mid-winter snow thickness value was high, the number of freeze-thaw days was the closest to the long-term average of northern Scandinavia, and the rate of thermal snow-melt in the subsequent spring was slow. The equations would need to be adjusted to take into account expected future changes to conditions such as shorter winters, less snow formation and increased frequency of air temperatures crossing 0 degrees C

Sub‐arctic river bank dynamics and driving processes during the open‐channel flow period

There is growing concern that rapidly changing climate in high latitudes may generate significant geomorphological changes that could mobilise floodplain sediments and carbon; however detailed investigations into the bank erosion process regimes of high latitude rivers remain lacking. Here we employ a combination of thermal and RGB colour time‐lapse photos in concert with water level, flow characteristics, bank sediment moisture and temperature, and topographical data to analyse river bank dynamics during the open‐channel flow period (the period from the rise of the spring snowmelt flood until the autumn low flow period) for a subarctic river in northern Finland (Pulmanki River). We show how variations of bank sediment temperature and moisture affect bank erosion rates and locations, how bank collapses relate to fluvial processes, and elucidate the seasonal variations and interlinkages between the different driving processes.We find that areas with high levels of groundwater content and loose sand layers were the most prone areas for bank erosion. Groundwater seeping caused continuous erosion throughout the study period, whereas erosion by flowing river water occurred during the peak of snowmelt flood. However, erosion also occurred during the falling phase of the spring flood, mainly due to mass failures. The rising phase of the spring flood therefore did not affect the river bank as much as its peak or receding phases. This is explained because the bank is resistant to erosion due to the prevalence of still frozen and drier sediments at the beginning of the spring flood. Overall, most bank erosion and deposition occurrences were observed during the low flow period after the spring flood. This highlights that spring melt, while often delivering the highest discharges, may not be the main driver of bank erosion in sub‐arctic meandering rivers

Permafrost degradation at two monitored palsa mires in north-west Finland

Palsas and peat plateaus are expected to disappear from many regions, including Finnish Lapland. However, detailed long-term monitoring data of the degradation process on palsas are scarce. Here, we present the results of the aerial photography time series analysis (1959–2021), annual real-time kinematic (RTK) GNSS and active layer monitoring (2007–2021), and annual unoccupied aerial system surveys (2016–2021) at two palsa sites (Peera and Laassaniemi, 68∘ N) located in north-west Finland. We analysed temporal trends of palsa degradation and their relation to climate using linear regression. At both sites, the decrease in palsa area by −77 % to −90 % since 1959 and height by −16 % to −49 % since 2007 indicate substantial permafrost degradation throughout the study periods. The area loss rates are mainly connected to winter air temperature changes at Peera and winter precipitation changes at Laassaniemi. The active layer thickness (ALT) has varied annually between 2007 and 2021 with no significant trend and is related mainly to the number of very warm days during summer, autumn rainfall of previous year, and snow depths at Peera. At Laassaniemi, the ALT is weakly related to climate and has been decreasing in the middle part of the palsa during the past 8 years despite the continuous decrease in palsa volume. Our findings imply that the ALT in the inner parts of palsas do not necessarily reflect the overall permafrost conditions and underline the importance of surface position monitoring alongside the active layer measurements. The results also showed a negative relationship between the ALT and snow cover onset, indicating the complexity of climate–permafrost feedbacks in palsa mires

Impacts of hydro-climatically varying years on ice growth and decay in a subarctic river

Predicting the future changes in river ice development and impacts on seasonal sediment transport requires more in-depth examination of present river ice cover growth processes. This paper therefore investigates: (1) the impacts of hydro-climatically varying years on river ice development in a Scandinavian subarctic meandering river and (2) the accuracy of existing analytical models for predicting ice thickness growth and ice decay. Stefan’s ice growth equation (version by Michel et al.) and Bilello’s ice decay equation are applied to varying hydro-climatic conditions experienced in the years 2013–2019. Estimates from these equations are compared with observed field conditions such as ice thicknesses, ice clearance dates and freeze-thaw days. Overall, the equations were most accurate in the winter of 2016–2017 when the maximum mid-winter snow thickness value was high, the number of freeze-thaw days was the closest to the long-term average of northern Scandinavia, and the rate of thermal snow-melt in the subsequent spring was slow. The equations would need to be adjusted to take into account expected future changes to conditions such as shorter winters, less snow formation and increased frequency of air temperatures crossing 0 °C

Flow Patterns and Morphological Changes in a Sandy Meander Bend during a FloodSpatially and Temporally Intensive ADCP Measurement Approach

The fluvio-geomorphological processes in meander bends are spatially uneven indistribution. Typically, higher velocities and erosion take place near the outer bank beyond thebend apex, while the inner bend point bar grows laterally towards the outer bank, increasing the bendamplitude. These dynamics maintain the meander evolution. Even though this development is foundin meandering rivers independent of soil or environmental characteristics, each river still seems tobehave unpredictably. The special mechanisms that determine the rate and occasion of morphologicalchanges remain unclear. The aim of this study is to offer new insights regarding flow-inducedmorphological changes in meander using a novel study approach. We focused on short-term andsmall-spatial-scale changes by conducting a spatially and temporally (daily) intensive survey duringa flood (a period of nine days) with an ADCP attached to a remotely controlled mini-boat. Based onour analysis, the flood duration and the rate of discharge increase and decrease seems to play keyroles in determining channel changes by controlling the flow velocities and depth and the backwatereffect may have notable influence on the morphological processes. We discuss themes such as theinteraction of inner and outer bend processes and the longer-term development of meander bends.</p