| 1. |
- Abbaszad Rafi, Abdolrahim, et al.
(författare)
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A facile route for concurrent fabrication and surface selective functionalization of cellulose nanofibers by lactic acid mediated catalysis
- 2023
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Ingår i: Scientific Reports. - : Springer Nature. - 2045-2322 .- 2045-2322. ; 13:1
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Tidskriftsartikel (refereegranskat)abstract
- Celulose nanofibers are lightweight, recycable, biodegradable, and renewable. Hence, there is a great interest of using them instead of fossil-based components in new materials and biocomposites. In this study, we disclose an environmentally benign (green) one-step reaction approach to fabricate lactic acid ester functionalized cellulose nanofibrils from wood-derived pulp fibers in high yields. This was accomplished by converting wood-derived pulp fibers to nanofibrillated “cellulose lactate” under mild conditions using lactic acid as both the reaction media and catalyst. Thus, in parallel to the cellulose nanofibril production, concurrent lactic acid-catalyzed esterification of lactic acid to the cellulose nanofibers surface occured. The direct lactic acid esterification, which is a surface selective functionalization and reversible (de-attaching the ester groups by cleavage of the ester bonds), of the cellulose nanofibrils was confirmed by low numbers of degree of substitution, and FT-IR analyses. Thus, autocatalytic esterification and cellulose hydrolysis occurred without the need of metal based or a harsh mineral acid catalysts, which has disadvantages such as acid corrosiveness and high recovery cost of acid. Moreover, adding a mineral acid as a co-catalyst significantly decreased the yield of the nanocellulose. The lactic acid media is successfully recycled in multiple reaction cycles producing the corresponding nanocellulose fibers in high yields. The disclosed green cellulose nanofibril production route is industrial relevant and gives direct access to nanocellulose for use in variety of applications such as sustainable filaments, composites, packaging and strengthening of recycled fibers.
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| 2. |
- Afewerki, Samson, et al.
(författare)
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Combined Catalysis for Engineering Bioinspired, Lignin-Based, Long-Lasting, Adhesive, Self-Mending, Antimicrobial Hydrogels
- 2020
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Ingår i: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 14:12, s. 17004-17017
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Tidskriftsartikel (refereegranskat)abstract
- The engineering of multifunctional biomaterials using a facile sustainable methodology that follows the principles of green chemistry is still largely unexplored but would be very beneficial to the world. Here, the employment of catalytic reactions in combination with biomass-derived starting materials in the design of biomaterials would promote the development of eco-friendly technologies and sustainable materials. Herein, we disclose the combination of two catalytic cycles (combined catalysis) comprising oxidative decarboxylation and quinone-catechol redox catalysis for engineering lignin-based multifunctional antimicrobial hydrogels. The bioinspired design mimics the catechol chemistry employed by marine mussels in nature. The resultant multifunctional sustainable hydrogels (1) are robust and elastic, (2) have strong antimicrobial activity, (3) are adhesive to skin tissue and various other surfaces, and (4) are able to self-mend. A systematic characterization was carried out to fully elucidate and understand the facile and efficient catalytic strategy and the subsequent multifunctional materials. Electron paramagnetic resonance analysis confirmed the long-lasting quinone-catechol redox environment within the hydrogel system. Initial in vitro biocompatibility studies demonstrated the low toxicity of the hydrogels. This proof-of-concept strategy could be developed into an important technological platform for the eco-friendly, bioinspired design of other multifunctional hydrogels and their use in various biomedical and flexible electronic applications.
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| 3. |
- Afewerki, Samson, 1985-, et al.
(författare)
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Sustainable and recyclable heterogenous palladium catalysts from rice husk-derived biosilicates for Suzuki-Miyaura cross-couplings, aerobic oxidations and stereoselective cascade carbocyclizations
- 2020
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Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322. ; 10
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Tidskriftsartikel (refereegranskat)abstract
- A new eco-friendly approach for the preparation of sustainable heterogeneous palladium catalysts from rice husk-derived biogenic silica (RHP-Si and RHU-Si). The designed heterogeneously supported palladium species (RHP-Si-NH2-Pd and RHU-Si-NH2-Pd) were fully characterized and successfully employed as catalysts for various chemical transformations (C–C bond-forming reactions, aerobic oxidations and carbocyclizations). Suzuki-Miyaura transformations were highly efficient in a green solvent system (H2O:EtOH (1:1) with excellent recyclability, providing the cross-coupling products with a wide range of functionalities in high isolated yields (up to 99%). Palladium species (Pd(0)-nanoparticles or Pd(II)) were also efficient catalysts in the green aerobic oxidation of an allylic alcohol and a co-catalytic stereoselective cascade carbocyclization transformation. In the latter case, a quaternary stereocenter was formed with excellent stereoselectivity (up to 27:1 dr).
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| 4. |
- Ali, Hasan, 1985-, et al.
(författare)
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Noise-dependent bias in quantitative STEM-EMCD experiments revealed by bootstrapping
- 2024
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Ingår i: Ultramicroscopy. - : Elsevier. - 0304-3991 .- 1879-2723. ; 257
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Tidskriftsartikel (refereegranskat)abstract
- Electron magnetic circular dichroism (EMCD) is a powerful technique for estimating element-specific magnetic moments of materials on nanoscale with the potential to reach atomic resolution in transmission electron microscopes. However, the fundamentally weak EMCD signal strength complicates quantification of magnetic moments, as this requires very high precision, especially in the denominator of the sum rules. Here, we employ a statistical resampling technique known as bootstrapping to an experimental EMCD dataset to produce an empirical estimate of the noise-dependent error distribution resulting from application of EMCD sum rules to bcc iron in a 3-beam orientation. We observe clear experimental evidence that noisy EMCD signals preferentially bias the estimation of magnetic moments, further supporting this with error distributions produced by Monte-Carlo simulations. Finally, we propose guidelines for the recognition and minimization of this bias in the estimation of magnetic moments.
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| 5. |
- Ali, Hasan, 1985-, et al.
(författare)
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Single scan STEM-EMCD in 3-beam orientation using a quadruple aperture
- 2023
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Ingår i: Ultramicroscopy. - : Elsevier BV. - 0304-3991 .- 1879-2723. ; 251
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Tidskriftsartikel (refereegranskat)abstract
- The need to acquire multiple angle-resolved electron energy loss spectra (EELS) is one of the several critical challenges associated with electron magnetic circular dichroism (EMCD) experiments. If the experiments are performed by scanning a nanometer to atomic-sized electron probe on a specific region of a sample, the precision of the local magnetic information extracted from such data highly depends on the accuracy of the spatial registration between multiple scans. For an EMCD experiment in a 3-beam orientation, this means that the same specimen area must be scanned four times while keeping all the experimental conditions same. This is a non-trivial task as there is a high chance of morphological and chemical modification as well as non-systematic local orientation variations of the crystal between the different scans due to beam damage, contamination and spatial drift. In this work, we employ a custom-made quadruple aperture to acquire the four EELS spectra needed for the EMCD analysis in a single electron beam scan, thus removing the above-mentioned complexities. We demonstrate a quantitative EMCD result for a beam convergence angle corresponding to sub-nm probe size and compare the EMCD results for different detector geometries.
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| 6. |
- Alimohammadzadeh, Rana, et al.
(författare)
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Direct Organocatalytic Thioglycolic Acid Esterification of Cellulose Nanocrystals : A simple entry to click chemistry on the surface of nanocellulose
- 2022
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Ingår i: Carbohydrate Polymer Technologies and Applications. - : Elsevier BV. - 2666-8939. ; 3
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Tidskriftsartikel (refereegranskat)abstract
- The mild and simple direct organocatalytic esterification of cellulose nanocrystals (CNC) and nanocellulose-based materials (e.g. foams and films) with thioglycolic acid (TGA) is disclosed. The transformation gives the corresponding thiol group (-SH) functionalized crystalline nanocellulose (CNC-SH) using simple, naturally occurring, and non-toxic organic acids (e.g. tartaric acid) as catalysts. We also discovered that the direct esterification of cellulose with TGA is autocatalytic (i.e. the TGA is catalyzing its own esterification). The introduction of the -SH functionality at the nanocellulose surface opens up for further selective applications. This was demonstrated by attaching organic catalysts and fluorescent molecules, which are useful as sensors, to the CNC-SH surface by thiol-ene click chemistry. Another application is to use the CNC-SH-based foam as a heterogeneous biomimetic reducing agent, which is stable during multiple recycles, for the copper-catalyzed alkyne-azide 1,3-dipolar cycloaddition (“click” reaction).
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| 7. |
- Asfaw, Habtom D., Dr. 1986-, et al.
(författare)
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Bio-derived hard carbon nanosheets with high rate sodium-ion storage characteristics
- 2022
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Ingår i: Sustainable Materials and Technologies. - : Elsevier. - 2214-9937. ; 32
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Tidskriftsartikel (refereegranskat)abstract
- Biomass is a sustainable precursor of hard carbons destined for use in sodium-ion batteries. This study explores the synthesis of hard carbon nanosheets (HCNS) from oxidized cork and impact of synthesis temperature on the hard carbon characteristics. An increase in the carbonization temperature from 1000 to 1500 °C generally leads to lower BET specific surface areas (~55 to 20 m2 g−1) and d002 interlayer spacing (~ 4.0 to 3.7 Å). The effect of synthesis temperature is reflected in the initial coulombic efficiency (iCE) which increases from 72% at 1000 °C to 88% at 1500 °C, as a result of the decrease in surface area, and structural defects in the hard carbon as verified using Raman scattering. The impact of cycling temperature (~25, 30 and 55 °C) on the rate capability and long-term cycling is investigated using high precision coulometry cycler. For a galvanostatic test at 20 mA g−1 and ~ 25 °C, a reversible capacity of 276 mAh g−1 is observed with an iCE of ~88%. Increasing cycling temperature enhances the rate performance, but slightly lowers the iCE (~86% at 30 °C and ~ 81% at 55 °C). At 20 mA g−1, the reversible capacities obtained at 30 °C and 55 °C are on average ~ 260 and ~ 270 mAh g−1, respectively. For constant-current constant-voltage (CCCV) tests conducted at 30 °C, reversible capacities ranging from 252 to 268, 247–252, and 237–242 mAh g−1 can be obtained at 10, 100, and 1000 mA g−1, respectively. The respective capacities obtained at 55 °C are about 272–290, 260–279, and 234–265 mAh g−1 at 10, 100 and 1000 mA g−1. The applicability of the HCNS electrodes is eventually evaluated in full-cells with Prussian white cathodes, for which a discharge capacity of 152 mAh g−1 is obtained with an iCE of ~90%.
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| 8. |
- Asfaw, Habtom Desta, Dr. 1986-, et al.
(författare)
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Facile synthesis of hard carbon microspheres from polyphenols for sodium-ion batteries : insight into local structure and interfacial kinetics
- 2020
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Ingår i: Materials Today Energy. - : Elsevier BV. - 2468-6069. ; 18
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Tidskriftsartikel (refereegranskat)abstract
- Hard carbons are the most promising negative active materials for sodium ion storage. In this work, a simple synthesis approach is proposed to produce hard carbon microspheres (CMSs) (with a mean diameter of ~1.3 μm) from resorcinol-formaldehyde precursors produced via acid-catalyzed polycondensation reaction. Samples prepared at 1200, 1400, and 1500 oC showed different electrochemical behavior in terms of reversible capacity, initial coulombic efficiency (iCE), and the mechanism of sodium ion storage. The specific capacity contributions from the flat voltage profile (<0.1 V) and the sloping voltage region (0.1–1 V) showed strong correlation to the local structure (and carbonization temperature) determined by the interlayer spacing (d002) and the Raman ID/IG ratio of the hard carbons (HCs) and the rate of cycling. Electrochemical tests indicated that the HC synthesized at 1500 oC performed best with an iCE of 85–89% and a reversible capacity of 300–340 mAh g−1 at 10 mA g−1, with the majority of charge stored below 0.1 V. The d002 and the ID/IG ratio for the sample were ~3.7 Å and ~1.27, respectively, parameters indicative of the ideal local structure in HCs required for optimum performance in sodium-ion cells. In addition, galvanostatic tests on three-electrode half-cells cells revealed that sodium metal plating occurred as cycling rates were increased beyond 80 mA g−1 leading to considerably high capacity and poor coulombic efficiency, a point that must be considered in full-cell batteries. Pairing the hard CMS electrodes with Prussian white positive electrode, a proof-of-concept cell could provide a specific capacity of almost 100 mAh g−1 maintained for more than 50 cycles with a nominal voltage of 3 V.
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| 9. |
- Cardenas, Edgar, et al.
(författare)
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Microstructural evolution of condensed aggregates during the crystallization of ZSM-5 from a heterogeneous system
- 2021
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Ingår i: Journal of Crystal Growth. - : Elsevier. - 0022-0248 .- 1873-5002. ; 568–569
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Tidskriftsartikel (refereegranskat)abstract
- The microstructural evolution of precursors of ZSM-5 zeolite crystallized from a heterogeneous system using fumed silica, sodium aluminate and tetrapropylammonium ions as reagents is investigated. Entities previously described by Ren et al. (Chem. Mater. 2012, 24, 10, 1726–1737) as condensed aggregates, were extensively studied using scanning electron microscopy, and energy dispersive spectroscopy. It was observed that the condensed aggregates first comprise a core of nanocrystals that is enveloped by a shell of amorphous gel phase. During crystallization, the amorphous shell surrounding the core is converted into ZSM-5 crystals that grow to a film surrounding the core. The crystals in the film grow competitively with nutrients provided by the liquid phase from the surroundings, while the nanocrystals in the core show little or no signs of growth.
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| 10. |
- Deiana, Luca, et al.
(författare)
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Artificial Arthropod Exoskeletons/Fungi Cell Walls Integrating Metal and Biocatalysts for Heterogeneous Synergistic Catalysis of Asymmetric Cascade Transformations
- 2023
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Ingår i: ChemCatChem. - : John Wiley & Sons. - 1867-3880 .- 1867-3899. ; 15:15
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Tidskriftsartikel (refereegranskat)abstract
- A novel and sustainable tandem-catalysis system for asymmetric synthesis is disclosed, which is fabricated by bio-inspired self-assembly of artificial arthropod exoskeletons (AAEs) or artificial fungi cell walls (AFCWs) containing two different types of catalysts (enzyme and metal nanoparticles). The heterogeneous integrated enzyme/metal nanoparticle AAE/AFCW systems, which contain chitosan as the main structural component, co-catalyze dynamic kinetic resolution of primary amines via a tandem racemization/enantioselective amidation reaction process to give the corresponding amides in high yields and excellent ee. The heterogeneous AAE/AFCW systems display successful heterogeneous synergistic catalysis at the surfaces since they can catalyze multiple reaction cycles without metal leaching. The use of natural-based and biocompatible structural components makes the AAE/AFCW systems fully biodegradable and renewable, thus fulfilling important green chemistry requirements.
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| 11. |
- Deiana, Luca, et al.
(författare)
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Artificial plant cell walls as multi-catalyst systems for enzymatic cooperative asymmetric catalysis in non-aqueous media
- 2021
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Ingår i: Chemical Communications. - : Royal Society of Chemistry (RSC). - 1359-7345 .- 1364-548X. ; 57:70, s. 8814-8817
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Tidskriftsartikel (refereegranskat)abstract
- The assembly of cellulose-based artificial plant cell wall (APCW) structures that contain different types of catalysts is a powerful strategy for the development of cascade reactions. Here we disclose an APCW catalytic system containing a lipase enzyme and nanopalladium particles that transform a racemic amine into the corresponding enantiomerically pure amide in high yield via a dynamic kinetic resolution.
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| 12. |
- Deiana, Luca, et al.
(författare)
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Cellulose-Supported Heterogeneous Gold-Catalyzed Cycloisomerization Reactions of Alkynoic Acids and Allenynamides
- 2023
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Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 13:15, s. 10418-10424
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Tidskriftsartikel (refereegranskat)abstract
- Herein, we describe efficient nanogold-catalyzed cycloisomerization reactions of alkynoic acids and allenynamides to enol lactones and dihydropyrroles, respectively (the latter via an Alder-ene reaction). The gold nanoparticles were immobilized on thiol-functionalized microcrystalline cellulose and characterized by electron microscopy (HAADF-STEM) and by XPS. The thiol-stabilized gold nanoparticles (Au-0) were obtained in the size range 1.5-6 nm at the cellulose surface. The robust and sustainable cellulose-supported gold nanocatalyst can be recycled for multiple cycles without losing activity.
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| 13. |
- Dürr, Robin N., et al.
(författare)
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Clearing Up Discrepancies in 2D and 3D Nickel Molybdate Hydrate Structures
- 2024
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 63:5
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Tidskriftsartikel (refereegranskat)abstract
- When electrocatalysts are prepared, modification of the morphology is a common strategy to enhance their electrocatalytic performance. In this work, we have examined and characterized nanorods (3D) and nanosheets (2D) of nickel molybdate hydrates, which previously have been treated as the same material with just a variation in morphology. We thoroughly investigated the materials and report that they contain fundamentally different compounds with different crystal structures, chemical compositions, and chemical stabilities. The 3D nanorod structure exhibits the chemical formula NiMoO4·0.6H2O and crystallizes in a triclinic system, whereas the 2D nanosheet structures can be rationalized with Ni3MoO5–0.5x(OH)x·(2.3 – 0.5x)H2O, with a mixed valence of both Ni and Mo, which enables a layered crystal structure. The difference in structure and composition is supported by X-ray photoelectron spectroscopy, ion beam analysis, thermogravimetric analysis, X-ray diffraction, electron diffraction, infrared spectroscopy, Raman spectroscopy, and magnetic measurements. The previously proposed crystal structure for the nickel molybdate hydrate nanorods from the literature needs to be reconsidered and is here refined by ab initio molecular dynamics on a quantum mechanical level using density functional theory calculations to reproduce the experimental findings. Because the material is frequently studied as an electrocatalyst or catalyst precursor and both structures can appear in the same synthesis, a clear distinction between the two compounds is necessary to assess the underlying structure-to-function relationship and targeted electrocatalytic properties.
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| 14. |
- Eliasson, Nora, et al.
(författare)
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Ultrafast Dynamics in Cu-Deficient CuInS2 Quantum Dots : SubBandgap Transitions and Self-Assembled Molecular Catalysts
- 2021
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 125:27, s. 14751-14764
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Tidskriftsartikel (refereegranskat)abstract
- The photophysical properties of Cu-deficient Cu01.2In1Sx quantum dots synthesized through a facile aqueous-based procedure have been investigated. Transient absorption experiments were carried out probing in the UV-vis, near-IR, and mid-IR regions, with the aim to (i) study the photophysical properties of the quantum dots and (ii) monitor kinetics of electron transfer to a molecular catalyst. When pumping subbandgap transitions, negative (bleach) signals were observed that were spectrally and kinetically distinct from those observed with bandgap pump wavelengths. Herein, these distinct contributions are suggested to result from the overlapping bleaching of state filling electrons and trapped holes. Such an interpretation highlights the importance of considering the hole-contributions to the bleach for the proper determination of carrier kinetics in similar systems. A model complex of the [Fe-2]-hydrogenase active site was introduced to explore the potential of the quantum dots as photosensitizers for molecular catalysts. The quantum dot photoluminescence was quenched upon catalyst addition, and direct evidence of the singly reduced catalyst was found by transient absorption in the UV-vis and mid-IR. The catalyst accepted reducing equivalents on a subpicosecond time scale upon photoexcitation of the quantum dots, despite no covalent linking chemistry being applied. This implies that charge transfer is not limited by diffusion rates, thus confirming the presence of spontaneous quantum dot and catalyst self-assembly.
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| 15. |
- Fan, Lizhou, et al.
(författare)
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Promoting the Fe(VI) active species generation by structural and electronic modulation of efficient iron oxide based water oxidation catalyst without Ni or Co
- 2020
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Ingår i: Nano Energy. - : Elsevier BV. - 2211-2855 .- 2211-3282. ; 72
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Tidskriftsartikel (refereegranskat)abstract
- Fe is considered as a promising alternative for OER catalysts owing to its high natural abundance and low cost. Due to the low conductivity and sluggish catalytic kinetics, the catalytic efficiency of Fe-rich catalysts is far from less abundant Ni, Co-rich alternatives and has been hardly improved without the involvement of Ni or Co. The lower activity of Fe-rich catalysts renders the real active center of state-of-the-art NiFe, CoFe catalyst in long-term scientific debate, despite of detection of Fe-based active intermediates in these catalysts during catalytic process. In the present work, we fabricated a series of sub-5 nm Fe1-yCryOx nanocatalysts via a simple solvothermal method, achieving systematically promoted high-valent Fe(VI) species generation by structural and electronic modulation, displaying highly active OER performance without involvement of Ni or Co. Detailed investigation revealed that the high OER activity is related to the ultrasmall nanoparticle size that promotes abundant edge- and corner-site exposure at catalyst surface, which involves in OER as highly reactive site; and the incorporated Cr ions that remarkably accelerate the charge transfer kinetics, providing an effective conduit as well as suitable host for high-valent active intermediate. This work reveals the structural prerequisites for efficient Fe-rich OER catalyst fabrication, inspiring deeper understanding of the structure-activity relationship as well as OER mechanism of Fe-based catalysts.
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| 16. |
- Guo, Yaxiao, et al.
(författare)
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Molybdenum and boron synergistically boosting efficient electrochemical nitrogen fixation
- 2020
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Ingår i: Nano Energy. - : Elsevier Ltd. - 2211-2855 .- 2211-3282. ; 78
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Tidskriftsartikel (refereegranskat)abstract
- Ammonia production consumes ~2% of the annual worldwide energy supply, therefore strategic alternatives for the energy-intensive ammonia synthesis through the Haber-Bosch process are of great importance to reduce our carbon footprint. Inspired by MoFe-nitrogenase and the energy-efficient and industrially feasible electrocatalytic synthesis of ammonia, we herein establish a catalytic electrode for artificial nitrogen fixation, featuring a carbon fiber cloth fully grafted by boron-doped molybdenum disulfide (B-MoS2/CFC) nanosheets. An excellent ammonia production rate of 44.09 μg h–1 cm–2 is obtained at −0.2 V versus the reversible hydrogen electrode (RHE), whilst maintaining one of the best reported Faradaic efficiency (FE) of 21.72% in acidic aqueous electrolyte (0.1 M HCl). Further applying a more negative potential of −0.25 V renders the best ammonia production rate of 50.51 μg h–1 cm–2. A strong-weak electron polarization (SWEP) pair from the different electron accepting and back-donating capacities of boron and molybdenum (2p shell for boron and 5d shell for molybdenum) is proposed to facilitate greatly the adsorption of non-polar dinitrogen gas via N≡N bond polarization and the first protonation with large driving force. In addition, for the first time a visible light driven photo-electrochemical (PEC) cell for overall production of ammonia, hydrogen and oxygen from water + nitrogen, is demonstrated by coupling a bismuth vanadate BiVO4 photo-anode with the B-MoS2/CFC catalytic cathode.
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| 17. |
- Görlin, Mikaela, et al.
(författare)
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Aging and Charge Compensation Effects of the Rechargeable Aqueous Zinc/Copper Hexacyanoferrate Battery Elucidated Using In Situ X-ray Techniques
- 2021
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 13:50, s. 59962-59974
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Tidskriftsartikel (refereegranskat)abstract
- The zinc/copper hexacyanoferrate (Zn/CuHCF) cell has gained attention as an aqueous rechargeable zinc-ion battery (ZIB) owing to its open framework, excellent rate capability, and high safety. However, both the Zn anode and the CuHCF cathode show unavoidable signs of aging during cycling, though the underlying mechanisms have remained somewhat ambiguous. Here, we present an in-depth study of the CuHCF cathode by employing various X-ray spectroscopic techniques. This allows us to distinguish between structure-related aging effects and charge compensation processes associated with electroactive metal centers upon Zn2+ ion insertion/deinsertion. By combining high-angle annular dark-field-scanning electron transmission microscopy, X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy, and elemental analysis, we reconstruct the picture of both the bulk and the surface. First, we identify a set of previously debated X-ray diffraction peaks appearing at early stages of cycling (below 200 cycles) in CuHCF. Our data suggest that these peaks are unrelated to hypothetical ZnxCu1–xHCF phases or to oxidic phases, but are caused by partial intercalation of ZnSO4 into graphitic carbon. We further conclude that Cu is the unstable species during aging, whose dissolution is significant at the surface of the CuHCF particles. This triggers Zn2+ ions to enter newly formed Cu vacancies, in addition to native Fe vacancies already present in the bulk, which causes a reduction of nearby metal sites. This is distinct from the charge compensation process where both the Cu2+/Cu+ and Fe3+/Fe2+ redox couples participate throughout the bulk. By tracking the K-edge fluorescence using operando XAS coupled with cyclic voltammetry, we successfully link the aging effect to the activation of the Fe3+/Fe2+ redox couple as a consequence of Cu dissolution. This explains the progressive increase in the voltage of the charge/discharge plateaus upon repeated cycling. We also find that SO42– anions reversibly insert into CuHCF during charge. Our work clarifies several intriguing structural and redox-mediated aging mechanisms in the CuHCF cathode and pinpoints parameters that correlate with the performance, which will hold importance for the development of future Prussian blue analogue-type cathodes for aqueous rechargeable ZIBs
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| 18. |
- Holm, Alexander, 1983-, et al.
(författare)
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A Water-Promoted Mars-van Krevelen Reaction Dominates Low-Temperature CO Oxidation over Au-Fe2O3 but Not over Au-TiO2
- 2024
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Ingår i: ACS Catalysis. - 2155-5435. ; 14:5, s. 3191-3197
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Tidskriftsartikel (refereegranskat)abstract
- We provide experimental evidence that is inconsistent with often proposed Langmuir−Hinshelwood (LH) mechanistic hypotheses for water-promoted CO oxidation over Au–Fe2O3. Passing CO and H2O, but no O2, over Au-γ-Fe2O3 at 25 °C, we observe significant CO2 production, inconsistent with LH mechanistic hypotheses. Experiments with H218O further show that previous LH mechanistic proposals cannot account for water-promoted CO oxidation over Au-γ-Fe2O3. Guided by density functional theory, we instead postulate a water-promoted Mars–van Krevelen (w-MvK) reaction. Our proposed w-MvK mechanism is consistent both with observed CO2 production in the absence of O2 and with CO oxidation in the presence of H218O and 16O2. In contrast, for Au-TiO2, our data is consistent with previous LH mechanistic hypotheses.
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| 19. |
- Kotronia, Antonia, et al.
(författare)
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Catalytically graphitized freestanding carbon foams for 3D Li-ion microbatteries
- 2020
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Ingår i: Journal of Power Sources Advances. - : Elsevier BV. - 2666-2485. ; 1
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Tidskriftsartikel (refereegranskat)abstract
- A long-range graphitic ordering in carbon anodes is desirable since it facilitates Li+ transport within the structure and minimizes irreversible capacity loss. This is of vital concern in porous carbon electrodes that exhibit high surface areas and porosity, and are used in 3D microbatteries. To date, it remains a challenge to graphitize carbon structures with extensive microporosity, since the two properties are considered to be mutually exclusive. In this article, carbon foams with enhanced graphitic ordering are successfully synthesized, while maintaining their bicontinuous porous microstructures. The carbon foams are synthesized from high internal phase emulsion-templated polymers, carbonized at 1000 °C and subsequently graphitized at 2200 °C. The key to enhancing the graphitization of the bespoke carbon foams is the incorporation of Ca- and Mg-based salts at early stages in the synthesis. The carbon foams graphitized in the presence of these salts exhibit higher gravimetric capacities when cycled at a specific current of 10 mA g−1 (140 mAh g−1) compared to a reference foam (105 mAh g−1), which amounts to 33% increase.
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| 20. |
- Kotronia, Antonia, et al.
(författare)
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Nature of the Cathode–Electrolyte Interface in Highly Concentrated Electrolytes Used in Graphite Dual-Ion Batteries
- 2021
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 13:3, s. 3867-3880
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Tidskriftsartikel (refereegranskat)abstract
- Dual-ion batteries (DIBs) generally operate beyond 4.7 V vs Li+/Li0 and rely on the intercalation of both cations and anions in graphite electrodes. Major challenges facing the development of DIBs are linked to electrolyte decomposition at the cathode–electrolyte interface (CEI), graphite exfoliation, and corrosion of Al current collectors. In this work, X-ray photoelectron spectroscopy (XPS) is employed to gain a broad understanding of the nature and dynamics of the CEI built on anion-intercalated graphite cycled both in highly concentrated electrolytes (HCEs) of common lithium salts (LiPF6, LiFSI, and LiTFSI) in carbonate solvents and in a typical ionic liquid. Though Al metal current collectors were adequately stable in all HCEs, the Coulombic efficiency was substantially higher for HCEs based on LiFSI and LiTFSI salts. Specific capacities ranging from 80 to 100 mAh g–1 were achieved with a Coulombic efficiency above 90% over extended cycling, but cells with LiPF6-based electrolytes were characterized by <70% Coulombic efficiency and specific capacities of merely ca. 60 mAh g–1. The poor performance in LiPF6-containing electrolytes is indicative of the continual buildup of decomposition products at the interface due to oxidation, forming a thick interfacial layer rich in LixPFy, POxFy, LixPOyFz, and organic carbonates as evidenced by XPS. In contrast, insights from XPS analyses suggested that anion intercalation and deintercalation processes in the range from 3 to 5.1 V give rise to scant or extremely thin surface layers on graphite electrodes cycled in LiFSI- and LiTFSI-containing HCEs, even allowing for probing anions intercalated in the near-surface bulk. In addition, ex situ Raman, SEM and TEM characterizations revealed the presence of a thick coating on graphite particles cycled in LiPF6-based electrolytes regardless of salt concentration, while hardly any surface film was observed in the case of concentrated LiFSI and LiTFSI electrolytes.
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| 21. |
- Kuhn, Joel, et al.
(författare)
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Tri-modal imaging of gold-dotted magnetic nanoparticles for magnetic resonance imaging, computed tomography and intravascular ultrasound : an in vitro study
- 2020
-
Ingår i: Nanomedicine. - : Future Medicine Ltd. - 1743-5889 .- 1748-6963. ; 15:25
-
Tidskriftsartikel (refereegranskat)abstract
- Aim: To examine the multimodal contrasting ability of gold-dotted magnetic nanoparticles (Au*MNPs) for magnetic resonance (MR), computed tomography (CT) and intravascular ultrasound (IVUS) imaging.Materials & methods: Au*MNPs were prepared by adapting an impregnation method, without using surface capping reagents and characterized (transmission electron microscopy, x-ray diffraction and Fourier-transform infrared spectroscopy) with theirin vitrocytotoxicity assessed, followed by imaging assessments.Results: The contrast-enhancing ability of Au*MNPs was shown to be concentration-dependent across MR, CT and IVUS imaging. The Au content of the Au*MNP led to evident increases of the IVUS signal.Conclusion: We demonstrated that Au*MNPs showed concentration-dependent contrast-enhancing ability in MRI and CT imaging, and for the first-time in IVUS imaging due to the Au content. These Au*MNPs are promising toward solidifying tri-modal imaging-based theragnostics.
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| 22. |
- Li, Shaowen, et al.
(författare)
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A Multiscale, Dynamic Elucidation of Li Solubility in the Alloy and Metallic Plating Process
- 2023
-
Ingår i: Advanced Materials. - 0935-9648 .- 1521-4095. ; 35:47
-
Tidskriftsartikel (refereegranskat)abstract
- Li-containing alloys and metallic deposits offer substantial Li+ storage capacities as alternative anodes to commercial graphite. However, the thermodynamically in sequence, yet kinetically competitive mechanism between Li solubility in the solid solution and intermediate alloy-induced Li deposition remains debated, particularly across the multiple scales. The elucidation of the mechanism is rather challenging due to the dynamic alloy evolution upon the non-equilibrium, transient lithiation processes under coupled physical fields. Here, influential factors governing Li solubility in the Li-Zn alloy are comprehensively investigated as a demonstrative model, spanning from the bulk electrolyte solution to the ion diffusion within the electrode. Through real-time phase tracking and spatial distribution analysis of intermediate alloy/Li metallic species at varied temperatures, current densities and particle sizes, the driving force of Li solubility and metallic plating along the Li migration pathway are probed in-depth. This study investigates the correlation between kinetics (pronounced concentration polarization, miscibility gap in lattice grains) and rate-limiting interfacial charge transfer thermodynamics in dedicating the Li diffusion into the solid solution. Additionally, the lithiophilic alloy sites with the balanced diffusion barrier and Li adsorption energy are explored to favor the homogeneous metal plating, which provides new insights for the rational innovation of high-capacity alloy/metallic anodes.
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| 23. |
- Li, Shaowen, et al.
(författare)
-
A Multiscale, Dynamic Elucidation of Li Solubility in the Alloy and Metallic Plating Process
- 2023
-
Ingår i: Advanced Materials. - : Wiley-VCH Verlagsgesellschaft. - 0935-9648 .- 1521-4095. ; 35:47
-
Tidskriftsartikel (refereegranskat)abstract
- Li-containing alloys and metallic deposits offer substantial Li+ storage capacities as alternative anodes to commercial graphite. However, the thermodynamically in sequence, yet kinetically competitive mechanism between Li solubility in the solid solution and intermediate alloy-induced Li deposition remains debated, particularly across the multiple scales. The elucidation of the mechanism is rather challenging due to the dynamic alloy evolution upon the non-equilibrium, transient lithiation processes under coupled physical fields. Here, influential factors governing Li solubility in the Li-Zn alloy are comprehensively investigated as a demonstrative model, spanning from the bulk electrolyte solution to the ion diffusion within the electrode. Through real-time phase tracking and spatial distribution analysis of intermediate alloy/Li metallic species at varied temperatures, current densities and particle sizes, the driving force of Li solubility and metallic plating along the Li migration pathway are probed in-depth. This study investigates the correlation between kinetics (pronounced concentration polarization, miscibility gap in lattice grains) and rate-limiting interfacial charge transfer thermodynamics in dedicating the Li diffusion into the solid solution. Additionally, the lithiophilic alloy sites with the balanced diffusion barrier and Li adsorption energy are explored to favor the homogeneous metal plating, which provides new insights for the rational innovation of high-capacity alloy/metallic anodes.
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| 24. |
- Mikheenkova, Anastasiia, et al.
(författare)
-
Ageing of High Energy Density Automotive Li-Ion Batteries : The Effect of Temperature and State-of-Charge
- 2023
-
Ingår i: Journal of the Electrochemical Society. - : The Electrochemical Society. - 0013-4651 .- 1945-7111. ; 170:8
-
Tidskriftsartikel (refereegranskat)abstract
- Lithium ion batteries (LIB) have become a cornerstone of the shift to electric transportation. In an attempt to decrease the production load and prolong battery life, understanding different degradation mechanisms in state-of-the-art LIBs is essential. Here, we analyze how operational temperature and state-of-charge (SoC) range in cycling influence the ageing of automotive grade 21700 batteries, extracted from a Tesla 3 long Range 2018 battery pack with positive electrode containing LiNixCoyAlzO2 (NCA) and negative electrode containing SiOx-C. In the given study we use a combination of electrochemical and material analysis to understand degradation sources in the cell. Herein we show that loss of lithium inventory is the main degradation mode in the cells, with loss of material on the negative electrode as there is a significant contributor when cycled in the low SoC range. Degradation of NCA dominates at elevated temperatures with combination of cycling to high SoC (beyond 50%).
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| 25. |
- Mikheenkova, Anastasiia, et al.
(författare)
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The Role of Oxygen in Automotive Grade Lithium-Ion Battery Cathodes : An Atomistic Survey of Ageing
- 2024
-
Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488 .- 2050-7496. ; 12:4, s. 2465-2478
-
Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- The rising demand for high-performance lithium-ion batteries, pivotal to electric transportation, hinges on key materials like the Ni-rich layered oxide LiNixCoyAlzO2 (NCA) used in cathodes. The present study investigates the redox mechanisms, with particular focus on the role of oxygen in commercial NCA electrodes, both fresh and aged under various conditions (aged cells have performed >900 cycles until a cathode capacity retention of ∼80%). Our findings reveal that oxygen participates in charge compensation during NCA delithiation, both through changes in transition metal (TM)–O bond hybridization and formation of partially reversible O2, the latter occurs already below 3.8 V vs. Li/Li+. Aged NCA material undergoes more significant changes in TM–O bond hybridization when cycling above 50% SoC, while reversible O2 formation is maintained. Nickel is found to be redox active throughout the entire delithiation and shows a more classical oxidation state change during cycling with smaller changes in the Ni–O hybridization. By contrast, Co redox activity relies on a stronger change in Co–O hybridization, with only smaller Co oxidation state changes. The Ni–O bond displays an almost twice as large change in its bond length on cycling as the Co–O bond. The Ni–O6 octahedra are similar in size to the Co–O6 octahedra in the delithiated state, but are larger in the lithiated state, a size difference that increases with battery ageing. These contrasting redox activities are reflected directly in structural changes. The NCA material exhibits the formation of nanopores upon ageing, and a possible connection to oxygen redox activity is discussed. The difference in interaction of Ni and Co with oxygen provides a key understanding of the mechanism and the electrochemical instability of Ni-rich layered transition metal oxide electrodes. Our research specifically highlights the significance of the role of oxygen in the electrochemical performance of electric-vehicle-grade NCA electrodes, offering important insights for the creation of next-generation long-lived lithium-ion batteries.
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| 26. |
- Mikheenkova, Anastasiia, et al.
(författare)
-
The role of oxygen in automotive grade lithium-ion battery cathodes : an atomistic survey of ageing
- 2024
-
Ingår i: Journal of Materials Chemistry A. - 2050-7488 .- 2050-7496. ; 12:4, s. 2465-2478
-
Tidskriftsartikel (refereegranskat)abstract
- The rising demand for high-performance lithium-ion batteries, pivotal to electric transportation, hinges on key materials like the Ni-rich layered oxide LiNixCoyAlzO2 (NCA) used in cathodes. The present study investigates the redox mechanisms, with particular focus on the role of oxygen in commercial NCA electrodes, both fresh and aged under various conditions (aged cells have performed >900 cycles until a cathode capacity retention of ∼80%). Our findings reveal that oxygen participates in charge compensation during NCA delithiation, both through changes in transition metal (TM)–O bond hybridization and formation of partially reversible O2, the latter occurs already below 3.8 V vs. Li/Li+. Aged NCA material undergoes more significant changes in TM–O bond hybridization when cycling above 50% SoC, while reversible O2 formation is maintained. Nickel is found to be redox active throughout the entire delithiation and shows a more classical oxidation state change during cycling with smaller changes in the Ni–O hybridization. By contrast, Co redox activity relies on a stronger change in Co–O hybridization, with only smaller Co oxidation state changes. The Ni–O bond displays an almost twice as large change in its bond length on cycling as the Co–O bond. The Ni–O6 octahedra are similar in size to the Co–O6 octahedra in the delithiated state, but are larger in the lithiated state, a size difference that increases with battery ageing. These contrasting redox activities are reflected directly in structural changes. The NCA material exhibits the formation of nanopores upon ageing, and a possible connection to oxygen redox activity is discussed. The difference in interaction of Ni and Co with oxygen provides a key understanding of the mechanism and the electrochemical instability of Ni-rich layered transition metal oxide electrodes. Our research specifically highlights the significance of the role of oxygen in the electrochemical performance of electric-vehicle-grade NCA electrodes, offering important insights for the creation of next-generation long-lived lithium-ion batteries.
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| 27. |
- Naim Katea, Sarmad, 1987-, et al.
(författare)
-
Nickel dot coating of NbC powder by solution processing
- 2020
-
Ingår i: Open Ceramics. - : Elsevier. - 2666-5395. ; 4
-
Tidskriftsartikel (refereegranskat)abstract
- A fast, low cost solution route to nickel dot coated NbC powder using Ni(NO3)26H2O, Ni(OAc)24H2O and triethanolamine (TEA) as precursors in methanol solvent was developed. After mixing the precursor solution with 50-300 nm sized NbC powder and evaporation of the solvent, heating to 150 oC, or higher, yielded NbC powder evenly covered with well-dispersed nickel metal dots, 6 to 25 nm in size, depending on the nickel loading and temperature. Coatings yielding 4 to 14 wt% nickel loading were studied at temperatures from 200 to 700 oC, using TG-DTA, XRD, SEM, XPS with Ar+-ion etching, TEM/DF, and STEM/HAADF/EDS.
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| 28. |
- Naim Katea, Sarmad, et al.
(författare)
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Niobium carbide – nickel-niobium alloy composites from a nickel coated powder : microstructural development during sintering
- 2021
-
Ingår i: Open Ceramics. - : Elsevier. - 2666-5395. ; 6
-
Tidskriftsartikel (refereegranskat)abstract
- The sintering of a 14 wt% nickel nano-dot coated NbC powder was investigated using dilatometry in combination with XRD, ToF-ERDA, PIXE, SEM-EDS/EBSD/TKD, and TEM-HAADF/EDS/EELS for analysis of samples heated to 1375, 1405 and 1500 °C, with a 30 min annealing. The main sintering step at 1110–1375 °C, was succeeded by a slower step, centred at 1405 °C, before the final smaller densification step to 1500 °C. NbC grain-growth took place on heating at 1500 °C for 30 min; from ca. 0.5–5 μm (average 1 μm) at 1375 and 1405 °C to ca. 5–30 μm (average 10 μm) 1500 °C for 30 min. The NbC0.91-0.94 phase showed a micro-hardness of 1700–2300 HV0.05. The binder phase consisted of the unprecedented textured c-Nb0.15Ni0.85 and h-Nb0.2Ni0.8 phases. The Nb–Ni binder phase yielded micro-hardness values of 1150–1250 (1375–1405 °C) to 810 HV0.05 (1500 °C, 30 min), which greatly exceeds nickel and is higher than Fe3Al.
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| 29. |
- Saadattalab, Vahid, et al.
(författare)
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Adsorption of volatile organic compounds on activated carbon with included iron phosphate
- 2023
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Ingår i: Carbon trends. - : Elsevier BV. - 2667-0569. ; 11
-
Tidskriftsartikel (refereegranskat)abstract
- Volatile organic compounds (VOCs) are often hazardous and need commonly to be removed from gas mixtures. Capture on activated carbon (AC) is one approach to achieving this. We hypothesized that the smallest pores on ACs and the inclusion of inorganic phosphates could enhance the low gas pressure uptake of two typical VOCs (acetone and isopropanol). To test this hypothesis, ACs were prepared by chemical activation of hydrochars with H3PO4 or a mixture of FeCl3 and H3PO4. The hydrochars had been prepared by hydrothermal carbonization of glucose. The ACs were characterized by XRD, IR, TGA, and the adsorption of N2, CO2, H2O, acetone, and isopropanol. The results showed that the ACs had comparably high adsorption of acetone and isopropanol at low vapor pressures. The low-pressure uptake (at 0.03 kPa) of isopropanol and acetone had values of up to 3.4 mmol/g and 2.2 mmol/g, respectively. This suggests that ACs containing iron phosphate could be of relevance for adsorption driven removal of VOC. It was also observed that the external surface area of the ACs containing iron phosphates increased upon secondary heat treatment in N2.
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| 30. |
- Saadattalab, Vahid, et al.
(författare)
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Blue hydrochars formed on hydrothermal carbonization of glucose using an iron catalyst
- 2022
-
Ingår i: Carbon Trends. - : Elsevier BV. - 2667-0569. ; 8
-
Tidskriftsartikel (refereegranskat)abstract
- We hypothesized that the morphology of the hydrochar from hydrothermal carbonization of glucose would be affected by Fe2+; and indeed, with such ions, large pieces of hydrochar formed that comprised aggregated spherical particles and blue and thin films. Thin carbonized films formed at the bottom of the autoclave liners or on TeflonTM tape used as a template. Free-standing films could be prepared by stretching the TeflonTM tape after the synthesis. The carbonized films that formed at the bottom of the autoclave adhered to spherical hydrochar particles. The blueness was ascribed to thin-film interference under white-light irradiation and related to the film thickness, which was about 200 nm. Analysis of transmission electron microscopy (TEM) images showed that the films consisted of a layered amorphous carbon. The amorphous and thin films were more carbonized than the amorphous carbon of the TEM grid, as derived via electron energy loss spectroscopy (EELS). Additional analysis of one of the thin films by X-ray photoelectron spectral analysis showed a higher carbon fraction than for bulk hydrochar, supporting the EELS analysis. We believe that the synthesis of thin films of hydrochar can open up new colloidal processing pathways, which could be useful in the preparation of carbon-based materials and alike.
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| 31. |
- Shal, ZeynabAlsadat Khatami, et al.
(författare)
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In-Situ Growth of Embryonic TS-1 on Amorphous Silica via Steam-Assisted Crystallization : Correlation of Structural Properties and Catalytic Performance of Embryonic, Crystalline, and Amorphous Titanosilicate Catalysts
- 2023
-
Ingår i: Crystal Growth & Design. - 1528-7483 .- 1528-7505. ; 23:7, s. 4883-4895
-
Tidskriftsartikel (refereegranskat)abstract
- In-situ growth of supported embryonic TS-1 zeolite (<10nm)on a silica support was achieved by steam-assisted crystallization(SAC). The use of low amounts of TPABr and steam at a moderate temperatureof 130 degrees C was the key factor to control partial transformationof silica into supported embryonic TS-1. Compared with the referencecrystalline TS-1, supported embryonic TS-1 exhibits a higher activityin dibenzothiophene (DBT) oxidation (TOF: 8-275 h(-1) vs 2.7-160 h(-1) at 30-98 degrees C),a higher resistance to poisoning by nitrogen-containing compounds,and a higher selectivity (>97%) in the productive utilization oftheoxidant in DBT oxidation. The activity of the amorphous titanosilicate(TOF: 21.2-210 h(-1) at 30-80 degrees C),the solid precursor of the SAC process, was higher than that of theembryonic and the crystalline TS-1. The analysis of the structuralproperties-catalytic performance of these catalysts showedan improved accessibility to defective Ti active sites Ti(OH)(OSi)(3) with higher catalytic activity. The results of thisstudy should be encouraging to unearth many other active amorphouscatalysts with the potential of industrial application.
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| 32. |
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| 33. |
- Sun, Rui, et al.
(författare)
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Highly Porous Amorphous Calcium Phosphate for Drug Delivery and Bio-Medical Applications
- 2020
-
Ingår i: Nanomaterials. - : MDPI. - 2079-4991. ; 10:1
-
Tidskriftsartikel (refereegranskat)abstract
- Amorphous calcium phosphate (ACP) has shown significant effects on the biomineralization and promising applications in bio-medicine. However, the limited stability and porosity of ACP material restrict its practical applications. A storage stable highly porous ACP with Brunauer–Emmett–Teller surface area of over 400 m2/g was synthesized by introducing phosphoric acid to a methanol suspension containing amorphous calcium carbonate nanoparticles. Electron microscopy revealed that the porous ACP was constructed with aggregated ACP nanoparticles with dimensions of several nanometers. Large angle X-ray scattering revealed a short-range atomic order of <20 Å in the ACP nanoparticles. The synthesized ACP demonstrated long-term stability and did not crystallize even after storage for over 14 months in air. The stability of the ACP in water and an α-MEM cell culture medium were also examined. The stability of ACP could be tuned by adjusting its chemical composition. The ACP synthesized in this work was cytocompatible and acted as drug carriers for the bisphosphonate drug alendronate (AL) in vitro. AL-loaded ACP released 25% of the loaded AL in the first 22 days. These properties make ACP a promising candidate material for potential application in biomedical fields such as drug delivery and bone healing.
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| 34. |
- Sun, Rui, et al.
(författare)
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The Effects of Additives on the Porosity and Stability of Amorphous Calcium Carbonate
- 2020
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Ingår i: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 292
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Tidskriftsartikel (refereegranskat)abstract
- Amorphous calcium carbonate (ACC) stabilized by various carboxylic additives was synthesized by incorporating the additives into an ACC suspension in methanol. The additives studied included polyacrylic acid, citric acid, adipic acid, 6-aminocaproic acid, 4-aminobutyric acid and hexanoic acid. The stabilized ACC samples (ACC-additives) exhibited similar characteristics to ACC alone. They appeared X-ray amorphous, contained characteristic infrared bands and had the same nanoparticle aggregated microstructure as ACC. The porosity of the ACC-additives was, however, markedly improved, with Brunauer-Emmett-Teller (BET) surface areas of up to ~640 m2/g. The BET surface area of ACC-citric acid was close to double that of a highly porous ACC sample. The structure and amount of the additive had a noticeable effect on the porosity of the ACC-additives. When the additive was adsorbed onto the surface of the ACC nanoparticles, their growth was restricted. The restricted growth reduced the size of the ACC nanoparticles, which increased the BET surface area of ACC. Finally, the long-term stability study revealed that the stability of all the ACC-additives was markedly enhanced when stored in ambient or semi-airtight conditions (in a closed falcon tube). In particular, ACC stabilized with adipic acid (ACC-AA-267) had excellent stability, remaining in an amorphous phase for more than one year under ambient conditions and retaining ~87% porosity for 48 weeks under semi-airtight conditions. The extremely high porosity and excellent long-term stability make these ACC-additives promising candidates for applications where porosity and stability are critical, such as those involving adsorption, bone regeneration or drug delivery.
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| 35. |
- Svensson, Fredric, et al.
(författare)
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Titanium phosphonate oxo-alkoxide "clusters": solution stability and facile hydrolytic transformation into nano titania
- 2020
-
Ingår i: RSC Advances. - : Royal Society of Chemistry (RSC). - 2046-2069. ; 10, s. 6873-6883
-
Tidskriftsartikel (refereegranskat)abstract
- Titanium (oxo-) alkoxide phosphonate complexes were synthesized using different titanium precursors and tert-butylphosphonic acid (tBPA) as molecular models for interaction between phosphonates and titania surfaces and to investigate the solution stability of these species. Reflux of titanium(iv) ethoxide or titanium(iv)(diisopropoxide)bis(2,4-pentadionate) with tert-butylphosphonic acid in toluene-ethanol mixture or acetone yielded seven titanium alkoxide phosphonate complexes; [Ti-5(mu(3)-O)(mu(2)-O)(mu-HOEt)(2)(mu-OEt)(3)(mu(2)-OEt)(mu(3)-tBPA)(3)(mu(3)-HtBPA)(mu(2)-tBPA)(2)(mu(2)-HtBPA)]center dot 3EtOH, 1, [Ti4O(mu-OEt)(5)(mu(2)-OEt)(7)(mu(3)-tBPA)], 2, [Ti-4(mu(2)-O)(2)(mu-OEt)(2)(mu-HOEt)(2)(mu(2)-tPBA)(2)(mu(2)-HtPBA)(6)]center dot 4EtOH, 3, [Ti-4(mu(2)-O)(2)(mu-OEt)(2)(mu-HOEt)(2)(mu(2)-tPBA)(2)(mu(2)-HtPBA)(6)]center dot 2EtOH, 4, [Ti-6(mu(2)-O)(mu(3)-O)(2)(mu(2)-OEt)(5)(mu-OEt)(6)(mu(3)-tBPA)(3)(mu(3)-HtBPA)], 5, [Ti-4(mu-(OPr)-O-i)(4)(acac)(4)(mu(2)-tBPA)(4)], 6 and [Ti-5(mu(4)-O)(mu(2)-O)(3)(mu(2)-OEt)(4)(mu-OEt)(6)(mu-HOEt)(mu(3)-tBPA)](2), 7. The binding mode of tBPA to the titanium oxo-core were either double or triple bridging or a combination of the two. No monodentate or chelating coordination was observed. P-31 NMR spectrometry of dissolved single crystals indicates that 1 and 5 retain their solid-state structures in solution, the latter even on moderate heating, while 6 and 7 dissolved into several other forms. The complexes were found to be sensitive towards hydrolysis, proceeding in a topotactic fashion with densification of the material into plates and lamellae resulting finally in "core-shell" nanoparticles with a crystalline core (anatase) and an amorphous outer shell upon contact with water at room temperature as observed by HRTEM and AFM analyses. P-31 NMR data supported degradation after addition of water to solutions of the complexes. Hydrolysis under different conditions affords complex oxide structures of different morphologies.
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| 36. |
- Valvo, Mario, et al.
(författare)
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Detecting voltage shifts and charge storage anomalies by iron nanoparticles in three-electrode cells based on converted iron oxide and lithium iron phosphate
- 2023
-
Ingår i: Electrochimica Acta. - : Elsevier BV. - 0013-4686 .- 1873-3859. ; 440
-
Tidskriftsartikel (refereegranskat)abstract
- Noticeable voltage shifts have been observed in the charge/discharge profiles of a three-electrode cell with a lithium metal reference electrode and having a deeply lithiated iron oxide (Fe/Li2O) negative electrode galvanostatically cycled in a limited potential range against a positive LiFePO4 counterpart. The origin of such shifts has been attributed to charge storage anomalies in the Fe/Li2O nanocomposite due to characteristic reduced Fe nanoparticle sizes. These shifts also affected the extreme points of the voltage profiles of the positive electrode, which was also independently monitored. A combined evaluation of voltage profile slippages with possible changes in internal resistance and/or Li+ inventory loss, including an aimed analysis of current interruptions at the end of each lithiation/de-lithiation half-cycle to monitor the internal resistance and diffusion resistance coefficient of the Fe/Li2O electrode, has enabled a clarification of its altered charge storage. An asymmetric behaviour of the Fe/Li2O electrode during Li+ uptake/release has been revealed, highlighting a progressive, diffusion-controlled-type voltage drift at low potentials vs. Li+/Li, and an unusual tendency to slight oxidation with capacitive variations during the reverse electrochemical processes at higher voltages, instead.
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| 37. |
- Veluru, Ramesh Naidu, et al.
(författare)
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Regio- and Stereoselective Carbon-Boron Bond Formation via Heterogeneous Palladium-Catalyzed Hydroboration of Enallenes
- 2023
-
Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 29:24
-
Tidskriftsartikel (refereegranskat)abstract
- A highly efficient regio- and stereoselective heterogeneous palladium-catalyzed hydroboration reaction of enallenes was developed. Nanopalladium immobilized on microcrystalline cellulose (MCC) was successfully employed as an efficient catalyst for the enallene hydroboration reaction. The nanopalladium particles were shown by HAADF-STEM to have an average size of 2.4 nm. The cellulose-supported palladium catalyst exhibits high stability and provides vinyl boron products in good to high isolated yields (up to 90 %). The nanopalladium catalyst can be efficiently recycled and it was demonstrated that the catalyst can be used in 7 runs with a maintained high yield (>80 %). The vinylboron compounds prepared from enallenes are important synthetic intermediates that can be used in various organic synthetic transformations.
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| 38. |
- Wang, Zhen, et al.
(författare)
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Layer-by-Layer Self-Assembled Nanostructured Electrodes for Lithium-Ion Batteries
- 2021
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Ingår i: Small. - : Wiley-VCH Verlag. - 1613-6810 .- 1613-6829. ; 17:6
-
Tidskriftsartikel (refereegranskat)abstract
- Gaining control over the nanoscale assembly of different electrode components in energy storage systems can open the door for design and fabrication of new electrode and device architectures that are not currently feasible. This work presents aqueous layer-by-layer (LbL) self-assembly as a route towards design and fabrication of advanced lithium-ion batteries (LIBs) with unprecedented control over the structure of the electrode at the nanoscale, and with possibilities for various new designs of batteries beyond the conventional planar systems. LbL self-assembly is a greener fabrication route utilizing aqueous dispersions that allow various Li+ intercalating materials assembled in complex 3D porous substrates. The spatial precision of positioning of the electrode components, including ion intercalating phase and electron-conducting phase, is down to nanometer resolution. This capable approach makes a lithium titanate anode delivering a specific capacity of 167 mAh g−1 at 0.1C and having comparable performances to conventional slurry-cast electrodes at current densities up to 100C. It also enables high flexibility in the design and fabrication of the electrodes where various advanced multilayered nanostructures can be tailored for optimal electrode performance by choosing cationic polyelectrolytes with different molecular sizes. A full-cell LIB with excellent mechanical resilience is built on porous insulating foams.
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| 39. |
- Yuan, Ning, et al.
(författare)
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Investigation of the Deactivation and Reactivation Mechanism of a Heterogeneous Palladium(II) Catalyst in the Cycloisomerization of Acetylenic Acids by In Situ XAS
- 2021
-
Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 11:5, s. 2999-3008
-
Tidskriftsartikel (refereegranskat)abstract
- A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst.
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| 40. |
- Zhang, Leiting, et al.
(författare)
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Elucidating the Humidity-Induced Degradation of Ni-Rich Layered Cathodes for Li-Ion Batteries
- 2022
-
Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 14:11, s. 13240-13249
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Tidskriftsartikel (refereegranskat)abstract
- Ni-rich layered oxides, in a general term of Li(NixCoyMn1–x–y)O2 (x > 0.5), are widely recognized as promising candidates for improving the specific energy and lowering the cost for next-generation Li-ion batteries. However, the high surface reactivity of these materials results in side reactions during improper storage and notable gas release when the cell is charged beyond 4.3 V vs Li+/Li0. Therefore, in this study, we embark on a comprehensive investigation on the moisture sensitivity of LiNi0.85Co0.1Mn0.05O2 by aging it in a controlled environment at a constant room-temperature relative humidity of 63% up to 1 year. We quantitatively analyze the gassing of the aged samples by online electrochemical mass spectrometry and further depict plausible reaction pathways, accounting for the origin of the gas release. Transmission electron microscopy reveals formation of an amorphous surface impurity layer of ca. 10 nm in thickness, as a result of continuous reactions with moisture and CO2 from the air. Underneath it, there is another reconstructed layer of ca. 20 nm in thickness, showing rock salt/spinel-like features. Our results provide insight into the complex interfacial degradation phenomena and future directions for the development of high-performance Ni-rich layered oxides.
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| 41. |
- Zheng, Zhiyao, et al.
(författare)
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Efficient Heterogeneous Copper-Catalyzed Alder-Ene Reaction of Allenynamides to Pyrrolines
- 2022
-
Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 12:3, s. 1791-1796
-
Tidskriftsartikel (refereegranskat)abstract
- Herein, we describe an efficient nanocopper-catalyzed Alder-ene reaction of allenynamides. The copper nanoparticles were immobilized on amino-functionalized microcrystalline cellulose. A solvent-controlled chemoselectivity of the reaction was observed, leading to the chemodivergent synthesis of pyrrolines (2,5-dihydropyrroles) and pyrroles. The heterogeneous copper catalyst exhibits high efficiency and good recyclability in the Alder-ene reaction, constituting a highly attractive catalytic system from an economical and environmental point of view.
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