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A light-assisted RAFT copolymerization protocol is established and investigated for the synthesis of 2-hydroxyethyl acrylate (HEA) / spiropyran acrylate (SPA) copolymers with enhanced SPA-contents. Radiation with visible light prevents the spiropyran (SP) motif from isomerizing into the open merocyanine (MC) form which can interfere with the polymerization process by abstracting a hydrogen atom from an active radical via its phenolic oxygen.
Assuntos
Acrilatos , Polímeros , Polimerização , NitrocompostosRESUMO
Controlled formation and breaking of weak chemical bonds is a versatile method for modifying the properties of materials. Anthracene [4+4] cycloadducts are a prime example that can be formed by light and opened by external forces. We address the theoretical description of mechanochemistry of these cycloadducts, where the standard constraint geometry simulates forces approach fails due to the lack of consideration of temperature. Explicit inclusion of external forces reveals the corresponding transition barriers that are clearly dominated by rupture of the [4+4] inter-anthracene bonds. Other bonds come into play at extremely large forces only, which cannot be expected to be reached under ambient conditions. The theoretical results are in line with the experimental rheology of [4+4]-linked anthracene polymers, which indicates reversible re-formation of [4+4] cycloaddition bonds with ultraviolet light after mechanochemical bond breaking due to applied shear stress.
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Hydrogenation is a promising technique to prepare black TiO2 (H-TiO2 ) for solar water splitting, however, there remain limitations such as severe preparation conditions and underexplored hydrogenation mechanisms to inefficient hydrogenation and poor photoelectrochemical (PEC) performance to be overcome for practical applications. Here, a room-temperature and rapid plasma hydrogenation (RRPH) strategy that realizes low-energy hydrogen ions of below 250 eV to fabricate H-TiO2 nanorods with controllable disordered shell, outperforming incumbent hydrogenations, is reported. The mechanisms of efficient RRPH and enhanced PEC activity are experimentally and theoretically unraveled. It is discovered that low-energy hydrogen ions with fast subsurface transport kinetics and shallow penetration depth features, enable them to directly penetrate TiO2 via unique multiple penetration pathways to form controllable disordered shell and suppress bulk defects, ultimately leading to improved PEC performance. Furthermore, the hydrogenation-property experiments reveal that the enhanced PEC activity is mainly ascribed to increasing band bending and bulk defect suppression, compared to reported H-TiO2 , a superior photocurrent density of 2.55 mA cm-2 at 1.23 VRHE is achieved. These findings demonstrate a sustainable strategy which offers great promise of TiO2 and other oxides to achieve further-improved material properties for broad practical applications.
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Friction and wear reduction by diamond-like carbon (DLC) in automotive applications can be affected by zinc-dialkyldithiophosphate (ZDDP), which is widely used in engine oils. Our experiments show that DLC's tribological behaviour in ZDDP-additivated oils can be optimised by tailoring its stiffness, surface nano-topography and hydrogen content. An optimal combination of ultralow friction and negligible wear is achieved using hydrogen-free tetrahedral amorphous carbon (ta-C) with moderate hardness. Softer coatings exhibit similarly low wear and thin ZDDP-derived patchy tribofilms but higher friction. Conversely, harder ta-Cs undergo severe wear and sub-surface sulphur contamination. Contact-mechanics and quantum-chemical simulations reveal that shear combined with the high local contact pressure caused by the contact stiffness and average surface slope of hard ta-Cs favour ZDDP fragmentation and sulphur release. In absence of hydrogen, this is followed by local surface cold welding and sub-surface mechanical mixing of sulphur resulting in a decrease of yield stress and wear.
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A stable passivation of surface dangling bonds underlies the outstanding friction properties of diamond and diamond-like carbon (DLC) coatings in boundary lubrication. While hydrogen is the simplest termination of a carbon dangling bond, fluorine can also be used as a monoatomic termination, providing an even higher chemical stability. However, whether and under which conditions a substitution of hydrogen with fluorine can be beneficial to friction is still an open question. Moreover, which of the chemical differences between C-H and C-F bonds are responsible for the change in friction has not been unequivocally understood yet. In order to shed light on this problem, we develop a density functional theory-based, nonreactive force field that describes the relevant properties of hydrogen- and fluorine-terminated diamond and DLC tribological interfaces. Molecular dynamics and nudged elastic band simulations reveal that the frictional stress at such interfaces correlates with the corrugation of the contact potential energy, thus ruling out a significant role of the mass of the terminating species on friction. Furthermore, the corrugation of the contact potential energy is almost exclusively determined by steric factors, while electrostatic interactions only play a minor role. In particular, friction between atomically flat diamond surfaces is controlled by the density of terminations, by the C-H and C-F bond lengths, and by the H and F atomic radii. For sliding DLC/DLC interfaces, the intrinsic atomic-scale surface roughness plays an additional role. While surface fluorination decreases the friction of incommensurate diamond contacts, it can negatively affect the friction performance of carbon surfaces that are disordered and not atomically flat. This work provides a general framework to understand the impact of chemical structure of surfaces on friction and to generate design rules for optimally terminated low-friction systems.
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Despite the pronounced polarity of C-F bonds, many fluorinated carbon compounds are hydrophobic: a controversial phenomenon known as "polar hydrophobicity". Here, its underlying microscopic mechanisms are explored by ab initio calculations of fluorinated and hydrogenated diamond (111) surfaces interacting with single water molecules. Gradient- and van der Waals-corrected density functional theory simulations reveal that "polar hydrophobicity" of the fully fluorinated surfaces is caused by a negligible surface/water electrostatic interaction. The densely packed C-F surface dipoles generate a short-range electric field that decays within the core repulsion zone of the surface and hence vanishes in regions accessible by adsorbates. As a result, water physisorption on fully F-terminated surfaces is weak (adsorption energies Ead < 0.1 eV) and dominated by van der Waals interactions. Conversely, the near-surface electric field generated by loosely packed dipoles on mixed F/H-terminated surfaces has a considerably longer range, resulting in a stronger water physisorption (Ead > 0.2 eV) that is dominated by electrostatic interactions. The suppression of electrostatic interactions also holds for perfluorinated molecular carbon compounds, thus explaining the prevalent hydrophobicity of fluorocarbons. In general, densely packed polar terminations do not always lead to short-range electric fields. For example, surfaces with substantial electron density spill-out give rise to electric fields with a much slower decay. However, electronic spill-out is limited in F/H-terminated carbon materials. Therefore, our ab initio results can be reproduced and rationalized by a simple classical point-charge model. Consequently, classical force fields can be used to study the wetting of F/H-terminated diamond, revealing a pronounced correlation between adsorption energies of single H2O molecules and water contact angles.
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The long-term stability of InGaN photoanodes in liquid environments is an essential requirement for their use in photoelectrochemistry. In this paper, we investigate the relationships between the compositional changes at the surface of n-type In(x)Ga(1-x)N (x â¼ 0.10) and its photoelectrochemical stability in phosphate buffer solutions with pH 7.4 and 11.3. Surface analyses reveal that InGaN undergoes oxidation under photoelectrochemical operation conditions (i.e., under solar light illumination and constant bias of 0.5 VRHE), forming a thin amorphous oxide layer having a pH-dependent chemical composition. We found that the formed oxide is mainly composed of Ga-O bonds at pH 7.4, whereas at pH 11.3 the In-O bonds are dominant. The photoelectrical properties of InGaN photoanodes are intimately related to the chemical composition of their surface oxides. For instance, after the formation of the oxide layer (mainly Ga-O bonds) at pH 7.4, no photocurrent flow was observed, whereas the oxide layer (mainly In-O bonds) at pH 11.3 contributes to enhance the photocurrent, possibly because of its reported high photocatalytic activity. Once a critical oxide thickness was reached, especially at pH 7.4, no significant changes in the photoelectrical properties were observed for the rest of the test duration. This study provides new insights into the oxidation processes occurring at the InGaN/liquid interface, which can be exploited to improve InGaN stability and enhance photoanode performance for biosensing and water-splitting applications.
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Selectivity and low power consumption are major challenges in the development of sophisticated gas sensor devices. A sensor system is presented that unifies selective sensor-gas interactions and energy-harvesting properties, using defined organic-inorganic hybrid materials. Simulations of chemical-binding interactions and the consequent electronic surface modulation give more insight into the complex sensing mechanism of selective gas detection.
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In situ transformations of selenidostannate frameworks in ionic liquids (ILs) were initiated by treatment of the starting phase K2[Sn2Se5] and the consecutive reaction products by means of temperature increase and/or amine addition. Along the reaction pathway, the framework dimensionalities of the five involved selenidostannate anions develop from 3D to 1D and back, both in top-down and bottom-up style. Addition of ethane-1,2-diamine (en) led to the reversion of the 2Dâ1D step from 2D-{[Sn24Se56](16-)} to 1D-{[Sn6Se14](4-)}. As rationalized by DFT investigations, the 2D anion is thermodynamically favored. Photoconductivity measurements reveal that all samples show Schottky contact behavior with absolute thresholds below 10 V. One of the samples exhibits conductive states within the energy range of visible photons.
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We present a linear-scaling method based on self-consistent charge non-orthogonal tight-binding. Linear scaling is achieved using a many-body expansion, which is adjusted dynamically to the instantaneous molecular configuration of a liquid. The method is capable of simulating liquids over large length and time scales, and also handles reactions correctly. Benchmarking on typical carbonate electrolytes used in Li-ion batteries displays excellent agreement with results from full tight-binding calculations. The decomposition slightly breaks the Hellmann-Feynman theorem, which is demonstrated by application to water. However, an additional correction also enables dynamical simulation in this case.