| 1. |
- Cao, Nan, et al.
(författare)
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On-surface synthesis of enetriynes
- 2023
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Ingår i: Nature Communications. - : NATURE PORTFOLIO. - 2041-1723. ; 14:1
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Tidskriftsartikel (refereegranskat)abstract
- Belonging to the enyne family, enetriynes comprise a distinct electron-rich all-carbon bonding scheme. However, the lack of convenient synthesis protocols limits the associated application potential within, e.g., biochemistry and materials science. Herein we introduce a pathway for highly selective enetriyne formation via tetramerization of terminal alkynes on a Ag(100) surface. Taking advantage of a directing hydroxyl group, we steer molecular assembly and reaction processes on square lattices. Induced by O-2 exposure the terminal alkyne moieties deprotonate and organometallic bis-acetylide dimer arrays evolve. Upon subsequent thermal annealing tetrameric enetriyne-bridged compounds are generated in high yield, readily self-assembling into regular networks. We combine high-resolution scanning probe microscopy, X-ray photoelectron spectroscopy and density functional theory calculations to examine the structural features, bonding characteristics and the underlying reaction mechanism. Our study introduces an integrated strategy for the precise fabrication of functional enetriyne species, thus providing access to a distinct class of highly conjugated pi-system compounds. Enetriynes, which belong to the enyne family, are characterized by a distinct electron-rich carbon-bonding scheme. Here, the authors report the formation of enetriynes with high selectivity by tetramerization of terminal alkynes on Ag(100).
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| 2. |
- Cao, Nan, et al.
(författare)
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The role of aromaticity in the cyclization and polymerization of alkyne-substituted porphyrins on Au(111)
- 2023
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Ingår i: Nature Chemistry. - : NATURE PORTFOLIO. - 1755-4330 .- 1755-4349.
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Tidskriftsartikel (refereegranskat)abstract
- Aromaticity is an established and widely used concept for the prediction of the reactivity of organic molecules. However, its role remains largely unexplored in on-surface chemistry, where the interaction with the substrate can alter the electronic and geometric structure of the adsorbates. Here we investigate how aromaticity affects the reactivity of alkyne-substituted porphyrin molecules in cyclization and coupling reactions on a Au(111) surface. We examine and quantify the regioselectivity in the reactions by scanning tunnelling microscopy and bond-resolved atomic force microscopy at the single-molecule level. Our experiments show a substantially lower reactivity of carbon atoms that are stabilized by the aromatic diaza[18]annulene pathway of free-base porphyrins. The results are corroborated by density functional theory calculations, which show a direct correlation between aromaticity and thermodynamic stability of the reaction products. These insights are helpful to understand, and in turn design, reactions with aromatic species in on-surface chemistry and heterogeneous catalysis. While aromaticity is a useful concept for assessing the reactivity of organic compounds, the connection between aromaticity and on-surface chemistry remains largely unexplored. Now, scanning probe experiments on cyclization reactions of porphyrins on Au(111) show that the peripheral carbon atoms outside of the aromatic 18-& pi; electron pathway exhibit a higher reactivity.
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| 3. |
- Fedina, Tatiana
(författare)
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Towards sustainability in additive manufacturing: material and process aspects
- 2023
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The acceptance of additive manufacturing (AM) depends on the quality of final parts and process repeatability. Recently, many studies have been dedicated to the establishment of the relationship between the process behavior and material performance. Phenomena such as laser-material interaction, melt pool dynamics, ejecta formation and particle movement behavior on a powder bed are of a particular interest for the AM community as these events directly influence the outcome of the process. Another aspect, which hinders the adoption of AM, is the need for cost-efficient powder materials, their sustainable processing and recycling. The research work presented in this thesis explores scientific aspects related to the above-mentioned topics, with a particular focus on the material and process behavior phenomena in powder bed fusion-laser melting (PBF-LM) and directed energy deposition (DED) processes. Paper A shows a comparative study of dissimilarly shaped gas and water atomized low alloy steel powders regarding their processability, packing capacities, particle movement behavior and powder performance in PBF-LM. The impact of chemical composition and morphology of the powders on the process behavior was revealed. Powder spattering and melt pool instabilities were discussed in detail. Paper B contains research on the particle movement and denudation behavior on a powder bed when using near-spherical and non-spherical steel powders. The influence of particle morphology on the dynamics of arbitrary-shaped powder particles was studied by applying an analytical correlation formula to calculate the drag force exerted on powder particles of various shape. Particle entrainment of gas and water atomized powders in front of the laser beam was measured, revealing a significant difference in the powder transfer towards the melt pool.Paper C explains the role of ejecta in the recycled powder and the changing behavior of the material due to ejecta pick-up. The impact of multiple powder recycling steps on the degradation of low alloy steel powder in laser powder bed fusion was studied. Oxygen content, particle size and ejecta occurrence gradually increased after each recycling step and were identified as the main contributors to the property alterations observed in the powder during recycling. In addition, a direct correlation between the increase in oxygen and more frequent spatter ejection with repeated recycling was established. Paper D focuses on the impact of powder aging on the degradation of AlSi10Mg powder during processing in PBF-LM. The analysis of the powder properties, affected by laser exposure and the aging procedure, showed a change of chemical and morphological characteristics of the powders in virgin and aged conditions. The oxygen content in the powders appeared to have a significant effect on the powders' surface appearance and light absorbance, gradually deteriorating the processability of the powders with the increase of oxygen level. Porosity occurrence and its influence on the mechanical properties of the powders was also studied, demonstrating a rapid decrease of ultimate tensile strength and elongation from virgin condition to aged.Papers E and F investigate the possibilities of iron ore waste reduction using Al powder as a reducing agent and a laser beam as a heat source. Paper E focuses on the Fe2O3-Al interaction behavior and extent of the iron ore reduction, whereas Paper F reports on the high-speed imaging investigation possibilities of laser beam-material surface interaction when processing Fe2O3-Al powders and an Fe2O3 powder-AlSI5 wire combination in DED. In-situ observation of various melt pool phenomena and exothermic reaction behavior of the material combinations using high-speed imaging was carried out. In addition to that, the influence of feed materials and laser power on the thermite reaction time was discussed in detail, showing their dissimilar behavior.All six papers include research on laser additive manufacturing using powder feedstocks. The papers discuss various phenomena regarding powder processability, recycling and laser beam-material interaction behavior in both PBF-LM and DED. High-speed imaging was used as the main tool to observe and study the above listed topics.
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| 4. |
- Garmroudi, Fabian, et al.
(författare)
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Anderson transition in stoichiometric Fe2VAl : high thermoelectric performance from impurity bands
- 2022
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Ingår i: Nature Communications. - : Springer Nature. - 2041-1723. ; 13:1
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Tidskriftsartikel (refereegranskat)abstract
- The mathematical conditions for the best thermoelectric is well known but never realised in real materials. Here, the authors propose the Anderson transition in a narrow impurity band as a physical realisation of this seemingly unrealisable scenario. Discovered more than 200 years ago in 1821, thermoelectricity is nowadays of global interest as it enables direct interconversion of thermal and electrical energy via the Seebeck/Peltier effect. In their seminal work, Mahan and Sofo mathematically derived the conditions for 'the best thermoelectric'-a delta-distribution-shaped electronic transport function, where charge carriers contribute to transport only in an infinitely narrow energy interval. So far, however, only approximations to this concept were expected to exist in nature. Here, we propose the Anderson transition in a narrow impurity band as a physical realisation of this seemingly unrealisable scenario. An innovative approach of continuous disorder tuning allows us to drive the Anderson transition within a single sample: variable amounts of antisite defects are introduced in a controlled fashion by thermal quenching from high temperatures. Consequently, we obtain a significant enhancement and dramatic change of the thermoelectric properties from p-type to n-type in stoichiometric Fe2VAl, which we assign to a narrow region of delocalised electrons in the energy spectrum near the Fermi energy. Based on our electronic transport and magnetisation experiments, supported by Monte-Carlo and density functional theory calculations, we present a novel strategy to enhance the performance of thermoelectric materials.
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| 5. |
- Pecunia, Vincenzo, et al.
(författare)
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Roadmap on energy harvesting materials
- 2023
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Ingår i: Journal of Physics. - : IOP Publishing. - 2515-7639. ; 6:4
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Tidskriftsartikel (refereegranskat)abstract
- Ambient energy harvesting has great potential to contribute to sustainable development and address growing environmental challenges. Converting waste energy from energy-intensive processes and systems (e.g. combustion engines and furnaces) is crucial to reducing their environmental impact and achieving net-zero emissions. Compact energy harvesters will also be key to powering the exponentially growing smart devices ecosystem that is part of the Internet of Things, thus enabling futuristic applications that can improve our quality of life (e.g. smart homes, smart cities, smart manufacturing, and smart healthcare). To achieve these goals, innovative materials are needed to efficiently convert ambient energy into electricity through various physical mechanisms, such as the photovoltaic effect, thermoelectricity, piezoelectricity, triboelectricity, and radiofrequency wireless power transfer. By bringing together the perspectives of experts in various types of energy harvesting materials, this Roadmap provides extensive insights into recent advances and present challenges in the field. Additionally, the Roadmap analyses the key performance metrics of these technologies in relation to their ultimate energy conversion limits. Building on these insights, the Roadmap outlines promising directions for future research to fully harness the potential of energy harvesting materials for green energy anytime, anywhere.
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| 6. |
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| 7. |
- Wang, Xiao-Ye, et al.
(författare)
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Exploration of pyrazine-embedded antiaromatic polycyclic hydrocarbons generated by solution and on-surface azomethine ylide homocoupling
- 2017
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Ingår i: Nature Communications. - : NATURE PUBLISHING GROUP. - 2041-1723. ; 8
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Tidskriftsartikel (refereegranskat)abstract
- Nanographenes, namely polycyclic aromatic hydrocarbons (PAHs) with nanoscale dimensions (amp;gt;1 nm), are atomically precise cutouts from graphene. They represent prime models to enhance the scope of chemical and physical properties of graphene through structural modulation and functionalization. Defined nitrogen doping in nanographenes is particularly attractive due to its potential for increasing the number of p-electrons, with the possibility of introducing localized antiaromatic ring elements. Herein we present azomethine ylide homocoupling as a strategy to afford internally nitrogen-doped, non-planar PAH in solution and planar nanographene on surfaces, with central pyrazine rings. Localized antiaromaticity of the central ring is indicated by optical absorption spectroscopy in conjunction with theoretical calculations. Our strategy opens up methods for chemically tailoring graphene and nanographenes, modified by antiaromatic dopants.
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| 8. |
- Yang, Biao, et al.
(författare)
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On-Surface Synthesis of Polyphenylene Wires Comprising Rigid Aliphatic Bicyclo[1.1.1]Pentane Isolator Units
- 2023
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Ingår i: Angewandte Chemie International Edition. - : WILEY-V C H VERLAG GMBH. - 1433-7851 .- 1521-3773. ; 62:19
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Tidskriftsartikel (refereegranskat)abstract
- Bicyclo[1.1.1]pentane (BCP) motifs are of growing importance to the pharmaceutical industry as sp(3)-rich bioisosteres of benzene rings and as molecular building blocks in materials science. Herein we explore the behavior of 1,3-disubstituted BCP moieties on metal surfaces by combining low-temperature scanning tunneling microscopy / non-contact atomic force microscopy studies with density functional theory modeling. We examine the configuration of individual BCP-containing precursors on Au(111), their supramolecular assembly and thermally activated dehalogenative coupling reactions, affording polymeric chains with incorporated electronically isolating units. Our studies not only provide the first sub-molecular insights of the BCP scaffold behavior on surfaces, but also extend the potential application of BCP derivatives towards integration in custom-designed surface architectures.
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