| 1. |
- Abrahams, I., et al.
(författare)
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A Combined Total Scattering and Simulation Approach to Analyzing Defect Structure in Bi3YO6
- 2010
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 1520-5002 .- 0897-4756. ; 22:15, s. 4435-4445
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Tidskriftsartikel (refereegranskat)abstract
- The defect structure and electrical properties of the fast oxide ion-conducting solid electrolyte delta-Bi3YO6 have been studied using a combination of total neutron scattering analysis, energy minimization methods, and AC impedance spectroscopy. Conventional structural analysis using the Rietveld method reveals the oxide ions to be distributed over three crystallographic sites at room temperature, with a small change in this distribution at 800 degrees C. Analysis of short-range correlations using a total neutron scattering approach yields information on Bi and Y coordination environments. Careful analysis of the angular distribution functions derived from reverse Monte Carlo modeling of the total scattering data reveals physical evidence for a predominance of vacancy ordering in this system. This ordering is confirmed as the lowest energy configuration in parallel energy minimization simulations.
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| 2. |
- Agostini, M., et al.
(författare)
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Polysulfide-containing Glyme-based Electrolytes for Lithium Sulfur Battery
- 2015
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 1520-5002 .- 0897-4756. ; 27:13, s. 4604-4611
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Tidskriftsartikel (refereegranskat)abstract
- A new comparative investigation of lithium sulfur cells employing a tetraethylene glycol dimethyl ether-lithium trifluoromethanesulfonate (TEGDME-LiCF3SO3) electrolyte charged by various polysulfide species (Li2S2, Li2S4, Li2S6, and Li2S8) is here reported. We carefully detect the effects of lithium polysulfide addition by originally combining X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The measurements clearly reveal how the polysulfide addition affects the nature and composition of the solid electrolyte interphase (SEI) in terms of precipitated S-based species determined by XPS. The study demonstrates that the SEI layer formed on the Li anode decreases in impedance and stabilizes by the presence of polysulfide. This, together with a buffer effect strongly mitigating the sulfur-cathode dissolution and the shuttle reaction, significantly improves the stability of the lithium-sulfur cell. The data here reported clearly suggest the polysulfide as an effective additive to enhance the performance of the lithium-sulfur battery (Graph Presented).
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| 3. |
- Agrios, Alexander George, et al.
(författare)
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Nanostructured composite films for dye-sensitized solar cells by electrostatic layer-by-layer deposition
- 2006
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 18:23, s. 5395-5397
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Tidskriftsartikel (refereegranskat)abstract
- The possibilities for making nanocomposite semiconductor films for DSC using the ELBL method was investigated. Coated slides were cut in half vertically giving two strips that can be subjected to different treatments for comparison. The electrode was heated to 450 °C for 30 min and then Cooled to 80 °C. Scanning electron microscopy of a sintered film with 5 cycles of TiO2 nanoparticles shows that the particles are well distributed and completely cover the transparent conducting oxide substrate. Spectroscopic measurements of a dye-coated film in acetonitrile found a dye concentration within the film of 0.15 mM based on an extinction coefficient. The solar cell including a scattering layer had more than double the current of the transparent layer-only cell. It was observed that ELBL method can produce TiO2 films for DSC with high efficiencies at low thickness.
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| 4. |
- Andrén, Oliver C. J., et al.
(författare)
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Therapeutic Nanocarriers via Cholesterol Directed Self-Assembly of Well-Defined Linear-Dendritic Polymeric Amphiphiles
- 2017
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 29:9, s. 3891-3898
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Tidskriftsartikel (refereegranskat)abstract
- A novel platform of fluorescently labeled nanocarriers (NCs) is herein proposed based on amphiphilic linear-dendritic polymeric hybrids. These sophisticated polymers were synthesized with a high degree of structural control at a macro-molecular level, displayed hydrophobic cholesterol compartments as chain-terminus groups of the dendritic block and hydrophilic bifunctional linear poly(ethylene glycol) (PEG) block. Spherical supramolecular assemblies with therapeutically relevant properties were successfully achieved including (i) sizes in the region of 100 to 200 nm; (ii) narrow dispersity profile with values close to 0.12; and (iii) self-assembly down to nanomolar concentrations. The modular nature of the NCs permitted the encapsulation of single or dual anticancer drugs and in parallel provide intracellular fluorescent traceability. As polymer therapeutics, the NCs were proven to penetrate the cancerous cell membranes and deliver the cargo of drugs into the nuclei as well as the cytoplasm and mitochondria. The dual drug delivery of both doxorubicin (DOX) and triptolide substantially enhanced the therapeutic efficacy with a 63% significant increase against resistant breast cancer cells when compared to free DOX.
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| 5. |
- Anselmo, Ana Sofia, 1980-, et al.
(författare)
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Tuning the Vertical Phase Separation in Polyfluorene: Fullerene Blend Films by Polymer Functionalization
- 2011
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Ingår i: Chemistry of Materials. - Washington : American Chemical Society (ACS). - 1520-5002 .- 0897-4756. ; 23:9, s. 2295-2302
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Tidskriftsartikel (refereegranskat)abstract
- Achieving control over the nanomorphology of blend films of the fullerene derivative [6,6]-phenyl C61-butyric acid methyl ester, PCBM, with light-absorbing conjugated polymers is an important challenge in the development of efficient solution-processed photovoltaics. Here, three new polyfluorene copolymers are presented, tailored for enhanced miscibility with the fullerene through the introduction of polymer segments with modified side chains, which enhance the polymer's polar character. The composition of the spincoated polymer:PCBM films is analyzed with dynamic secondary ion mass spectrometry (dSIMS). The dSIMS depth profiles demonstrate compositional variations perpendicular to the surface plane, as a result of vertical phase separation, directed by the substrate. These variations propagate to a higher degree through the film for the polymers with a larger fraction of modified side chains. The surface composition of the films is studied by Near-edge X-ray absorption fine structure spectroscopy (NEXAFS). Quantitative analysis of the NEXAFS spectra through a linear combination fit with the spectra of the pure components yields the surface composition. The resulting blend ratios reveal polymer-enrichment of the film surface for all three blends, which also becomes stronger as the polar character of the polymer increases. Comparison of the NEXAFS spectra collected with two different sampling depths shows that the vertical composition gradient builds up already in the first nanometers underneath the surface of the films. The results obtained with this new series of polymers shed light on the onset of formation of lamellar structures in thin polymer:PCBM films prepared from highly volatile solvents.
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| 6. |
- Arcos, D., et al.
(författare)
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Ordered Mesoporous Microspheres for Bone Grafting and Drug Delivery
- 2009
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 21:6, s. 1000-1009
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Tidskriftsartikel (refereegranskat)abstract
- Bioactive microspheres with ordered mesoporous structure have been synthesized by means of the evaporation-induced self-assembly (EISA) method and following an aerosol-assisted route. The bioactive microspheres belong to the SiO2-CaO-P2O5 systems, and the mesoporous structure closely depends on the structure-directing agent as well as its interaction with the Ca2+ cations during the mesophase formation. Among the different tested surfactants, the triblock copolymer F127 leads to hexagonal ordered structures for low CaO contents, P123 leads to wormlike mesoporous structures for any CaO content, whereas the ionic surfactant cetyltrimethyl ammonium bromide (C16TAB) does not produce accessible mesopores at the external surface, for any CaO content. All the mesoporous SiO2-CaO-P2O5 microspheres develop an apatite like layer when reacting with simulated body fluid. Preliminary tests indicate the capability to load and release triclosan with kinetic profiles that depend on the pore structure, thus showing interesting features to be used in periodontal regenerative surgery and infection profilaxis.
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| 7. |
- Arnbjerg, Lene M., et al.
(författare)
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Structure and Dynamics for LiBH4-LiCl Solid Solutions
- 2009
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 21:24, s. 5772-5782
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Tidskriftsartikel (refereegranskat)abstract
- A Surprisingly high degree of structural and compositional dynamics is observed in the system LiBH4-LiCl as a function of temperature and time. Rietveld refinement of synchrotron radiation powder X-ray diffraction (SR-PXD) data reveals that Cl- readily substitutes for BH4- in the Structure of LiBH4. Prolonged heating a sample of LiBH4-LiCl (1:1 molar ratio) above the phase transition temperature and below the melting point (108 < T < 275 degrees C) can produce highly chloride substituted hexagonal lithium borohydride, h-Li(BH4)(l-x)Cl-x, e.g., x similar to 0.42, after heating from room temperature (RT) to 224 degrees C at 2.5 degrees C/min. LiCl has a higher solubility in h-LiBH4 its compared to orthorhombic lithium borohydride, o-LiBH4, which is illustrated by a LiBH4-LiCl (1:1) sample equilibrated at 245 degrees C for 24 days and left at RT for another 13 months. Rietveld refinement reveals that this sample contains o-Li(BH4)(0.91)Cl-0.09 and LiCl. This illustrates a significantly faster dissolution of LiCl in h-LiBH4 its compared to a slower segregation of LiCl from o-LiBH4, which is also demonstrated by in situ SR-PXD from three cycles of heating and cooling of the same Li(BH4)(0.91)Cl-0.09 sample. The substitution of the smaller Cl- for the larger BH4- ion is clearly observed as a reduction in the unit cell volume as a function of time and temperature. A significant stabilization of h-LiBH4 is found to depend on the degree of anion substitution. Variable temperature solid-state magic-angle spinning (MAS) Li-7 and B-13 NMR experiments oil pure LiBH4 show an increase in full width at half maximum (fwhm) when approaching the phase transition from o- to h-LiBH4, which indicates an increase of the relaxation rate (i.e. T-2 decreases). A less pronounced effect is observed for ion-substituted Li(BH4)(1-x)Cl-x, 0.09 < x < 0.42. The MAS NMR experiments also demonstrate a higher degree of motion in the hexagonal phase, i.e., fwhm is reduced by more than a Factor of 10 at the o- to h-LiBH4 phase transition.
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| 8. |
- Arvizu, Miguel A, et al.
(författare)
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Electrochromic W(1-x-y)Ti(x)lo(y)O(3) Thin Films Made by Sputter Deposition : Large Optical Modulation, Good Cycling Durability, and Approximate Color Neutrality
- 2017
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 29:5, s. 2246-2253
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Tidskriftsartikel (refereegranskat)abstract
- Tungsten oxide thin films are used in electrochromic devices such as variable-transmittance "smart windows" for energy efficient buildings with good indoor comfort. Two long-standing issues for WO3 thin films are their limited durability under electrochemical cycling and their blue color in transmission. Here, we show that both of these problems can be significantly alleviated by additions of titanium and molybdenum. We found that similar to 300 nm-thick films of sputter deposited W1-x-yTixMoyO3 are able to combine a midluminous transmittance modulation of 0.4 similar to 70% with good color neutrality and durability under extended electrochemical cycling. The Ti content should be similar to 10 at. % in order to achieve durability without impairing transmittance modulation significantly, and the Mo content preferably should be no larger than 6 at. % in order to maintain durability. Hence, our results give clear guidelines for making three-component mixed-oxide thin films that are suitable for electrochromic "smart windows".
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| 9. |
- Atluri, Rambabu, 1981-, et al.
(författare)
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Hydrothermal Phase Transformation of Bicontinuous Cubic Mesoporous Material AMS-6
- 2008
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 20:12, s. 3857–3866-
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Tidskriftsartikel (refereegranskat)abstract
- The controlled synthesis of ordered anionic surfactant templated mesoporous silica with cubic Ia3d̅ structure (AMS-6) is reported via prolonged periods of hydrothermal treatment (HT). The cubic Ia3d̅ mesophase transforms to hexagonal p6mm after 8 days of HT at 100 °C. Surprisingly, the hexagonal phase is stable only for a limited period after which a reversal to the cubic Ia3d̅ mesostructure is observed. Characterization methods such as powder X-ray diffraction (XRD), electron microscopy (SEM, TEM), N2-isotherms, magic-angle spinning (MAS) 29Si NMR spectroscopy, and thermogravimetric analysis (TGA) have been employed to follow structural and textural changes of the materials prepared. Data show that the resultant mesostructure and its textural properties are highly dependent on the period of HT with less unit-cell shrinkage on calcination after extensive HT. Furthermore, evidence of two different solid−solid phase mechanisms during HT is presented. The initial transition is consistent with a restructuring of the surfactant packing and a depletion of the organic moieties from the organo-silica wall as evident from 29Si NMR spectroscopy. The return to the bicontinuous cubic phase is driven by changes in charge matching at the organic−inorganic interface as a result of increases in the polymerization of the silica wall. The textural properties, and in particular the presence or absence of surface porosity, has been controlled through variations in hydrothermal treatment. These are associated with specific growth directions of cubic AMS-6 crystals. The synthetic method described allows us to easily prepare phase pure and intermediate mesostructured nanoparticles.
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| 10. |
- Bai, Sai, et al.
(författare)
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Reproducible Planar Heterojunction Solar Cells Based on One-Step Solution-Processed Methylammonium Lead Halide Perovskites
- 2017
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Ingår i: Chemistry of Materials. - : AMER CHEMICAL SOC. - 0897-4756 .- 1520-5002. ; 29:1, s. 462-473
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Tidskriftsartikel (refereegranskat)abstract
- Metal halide perovskites have been demonstrated as one of the most promising materials for low-cost and high-performance photovoltaic applications. However, due to the susceptible crystallization process of perovskite films on planar substrates and the high sensitivity of the physical and optoelectronic nature of the internal interfaces within the devices, researchers in different laboratories still experience poor reproducibility in fabricating efficient perovskite solar cells with planar heterojunction device structures. In this method paper, we present detailed information on the reagents, equipment, and procedures for the fabrication of planar perovskite solar cells in both "regular" n-i-p and "inverted" p-i-n architectures based on one-step solution-processed methylammonium lead triiodide (MAPbI(3)) perovskite films. We discuss key parameters affecting the crystallization of perovskite and the device interfaces. This method paper will provide a guideline for the reproducible fabrication of planar heterojunction solar cells based on MAPbI3 perovskite films. We believe that the shared experience on MA-based perovskite films and planar solar cells will be also useful for the optimization process of perovskites with varied compositions, and other emerging perovskite-based optoelectronic devices.
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| 11. |
- Banerjee, Hrishit, et al.
(författare)
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Cationic Effect on Pressure Driven Spin-State Transition and Cooperativity in Hybrid Perovskites
- 2016
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 28:22, s. 8379-8384
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Tidskriftsartikel (refereegranskat)abstract
- Hybrid or metal organic framework (MOP) perovskites of general composition, ABX(3), are known to show interesting properties that can lead to a variety of technological applications. Our first-principles study shows they are also potential candidates for exhibiting cooperative spin-state transitions upon application of external stimuli. We demonstrate this by considering two specific Fe-based MOF perovskites, namely dimethylammonium iron formate, [CH3NH2CH3][Fe(HCOO)(3)], and hydroxylammonium iron formate, [NH3OH][Fe(HCOO)(3)]. Both the compounds are found to undergo high-spin (S = 2) to low-spin (S = 0) transition at Fe(II) site upon application of moderate strength of hydrostatic pressure, along with large hysteresis. This spin-state transition is signaled by the changes in electronic, magnetic, and optical properties. We find both the transition pressure and the width of the hysteresis to be strongly dependent on the choice of A-site cation, dimethylammonium or hydroxylammonium, implying that tuning of spin-switching properties is achievable by chemical variation of the amine cation in the structure. Our findings open up novel functionalities in this family of materials of recent interest, which can have important usage in sensors and memory devices.
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| 12. |
- Bellani, Sebastiano, et al.
(författare)
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Graphene-Based Electrodes in a Vanadium Redox Flow Battery Produced by Rapid Low-Pressure Combined Gas Plasma Treatments
- 2021
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 33:11, s. 4106-4121
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Tidskriftsartikel (refereegranskat)abstract
- The development of high-power density vanadium redox flow batteries (VRFBs) with high energy efficiencies (EEs) is crucial for the widespread dissemination of this energy storage technology. In this work, we report the production of novel hierarchical carbonaceous nanomaterials for VRFB electrodes with high catalytic activity toward the vanadium redox reactions (VO2+/VO2+ and V2+/V3+). The electrode materials are produced through a rapid (minute timescale) low-pressure combined gas plasma treatment of graphite felts (GFs) in an inductively coupled radio frequency reactor. By systematically studying the effects of either pure gases (O-2 and N-2) or their combination at different gas plasma pressures, the electrodes are optimized to reduce their kinetic polarization for the VRFB redox reactions. To further enhance the catalytic surface area of the electrodes, single-/fewlayer graphene, produced by highly scalable wet-jet milling exfoliation of graphite, is incorporated into the GFs through an infiltration method in the presence of a polymeric binder. Depending on the thickness of the proton-exchange membrane (Nafion 115 or Nafion XL), our optimized VRFB configurations can efficiently operate within a wide range of charge/discharge current densities, exhibiting energy efficiencies up to 93.9%, 90.8%, 88.3%, 85.6%, 77.6%, and 69.5% at 25, 50, 75, 100, 200, and 300 mA cm(-2), respectively. Our technology is cost-competitive when compared to commercial ones (additional electrode costs < 100 (sic) m(-2)) and shows EEs rivalling the record-high values reported for efficient systems to date. Our work remarks on the importance to study modified plasma conditions or plasma methods alternative to those reported previously (e.g., atmospheric plasmas) to improve further the electrode performances of the current VRFB systems.
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| 13. |
- Bi, Chenghao, et al.
(författare)
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Stable CsPb1- xZn xI3Colloidal Quantum Dots with Ultralow Density of Trap States for High-Performance Solar Cells
- 2020
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 32:14, s. 6105-6113
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Tidskriftsartikel (refereegranskat)abstract
- All inorganic halide perovskites in the form of colloidal quantum dots (QDs) have come into people's view as one of the potential materials for the high-efficiency solar cells; nevertheless, the high surface trap density and poor stability of QDs restrict the performance improvement and application. Here, we obtain colloidal inorganic perovskite CsPb1-xZnxI3 QDs by the hot-injection synthesis process with the addition of ZnCl2. Synchrotron-based X-ray absorption fine structures demonstrate that the guest Zn2+ ions are doped into the CsPbI3 structure to improve the local ordering of the lattice of the perovskite, reducing the octahedral distortions. The increase of the Goldschmidt tolerance factor and the Pb-I bond energy also enhance the stability of the perovskite structure. Furthermore, the Cl- ions from ZnCl2 occupy the iodide vacancies of the perovskite to decrease the nonradiative recombination. The synergistic effect of doping and defect passivation makes for stable colloidal CsPb0.97Zn0.03I3 QDs with ultralow density of trap states. The champion solar cell based on the QDs shows a power conversion efficiency of 14.8% and a largely improved stability under ambient conditions.
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| 14. |
- Bilousov, Oleksandr V., et al.
(författare)
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Atomic Layer Deposition of Cubic and Orthorhombic Phase Tin Monosulfide
- 2017
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Ingår i: Chemistry of Materials. - : AMER CHEMICAL SOC. - 0897-4756 .- 1520-5002. ; 29:7, s. 2969-2978
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Tidskriftsartikel (refereegranskat)abstract
- Tin monosulfide (SnS) is a promising light-absorbing material with weak environmental constraints for application in thin film solar cells. In this paper, we present low-temperature atomic layer deposition (ALD) of high-purity SnS of both cubic and orthorhombic phases. Using tin(II) 2,4-pentanedionate [Sn(acac)(2)] and hydrogen sulfide (H2S) as precursors, controlled growth of the two polymorphs is achieved. Quartz crystal microbalance measurements are used to establish saturated conditions and show that the SnS ALD is self-limiting over temperatures from at least 80 to 160 degrees C. In this temperature window, a stable mass gain of 19 ng cm(-2) cycle(-1) is observed. The SnS thin film crystal structure and morphology undergo significant changes depending on the conditions. High-resolution transmission electron microscopy and X-ray diffraction demonstrate that fully saturated growth requires a large H2S dose and results in the cubic phase. Smaller H2S doses and higher temperatures favor the orthorhombic phase. The optical properties of the two polymorphs differ significantly, as demonstrated by spectroscopic ellipsometry. The orthorhombic phase displays a wide (0.3-0.4 eV) Urbach tail in the near-infrared region, ascribed to its nanoscale structural disorder and/or to sulfur vacancy-induced gap states. In contrast, the cubic phase is smooth and void-free and shows a well-defined, direct forbidden-type bandgap of 1.64 eV.
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| 15. |
- Bilousov, Oleksandr V., et al.
(författare)
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Substrate Effects on Crystal Phase in Atomic Layer Deposition of Tin Monosulfide
- 2021
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 33:8, s. 2901-2912
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Tidskriftsartikel (refereegranskat)abstract
- Obtaining single-phase tin monosulfide (SnS) films at low temperatures is challenging since cubic (π-SnS) and orthorhombic (α-SnS) polymorphs have similar energies of formation and grow under similar conditions. Here, we show that in atomic layer deposition (ALD) of polycrystalline SnS using tin(II) acetylacetonate and H2S precursors, the substrate surface greatly influences the SnS phase evolution. For example, a silicon (100) substrate, with a highly hydroxylated surface, favors the growth of α-SnS. Meanwhile, ozone treatment or preannealing of the same substrate leads to mainly π-SnS. Just a few ALD cycles of another oxide or sulfide can even more substantially alter the outcome. Substrates that favor α-SnS growth typically produce initially enhanced growth rates, while those promoting π-SnS are partially surface-poisoned by the acetylacetonate precursor ligands. Growth of either polymorph is self-sustained after its initiation, and the sustaining factor appears to be the surface–ligand interaction; π-SnS preferentially evolves on substrates and π-SnS surfaces that are rich in highly reactive dangling bonds, while chemically inert substrates and α-SnS surfaces promote α-SnS. While lattice matching is less central, the role of ligand bonding in SnS ALD also helps explain the previously reported phase dependence on growth temperature and H2S precursor dose and shows promise for area-selective ALD of SnS.
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| 16. |
- Björk, Jonas, et al.
(författare)
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Functionalizing MXenes by Tailoring Surface Terminations in Different Chemical Environments
- 2021
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Ingår i: Chemistry of Materials. - : American Chemical Society. - 0897-4756 .- 1520-5002. ; 33:23, s. 9108-9118
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Tidskriftsartikel (refereegranskat)abstract
- Two-dimensional metal carbides and nitrides-MXenes-represent a group of materials which have attained growing attention over the last decade due to their chemical versatility, making them highly promising in areas such as energy storage, superconductivity, and heterogenous catalysis. Surface terminations are a natural consequence of the MXene synthesis, conventionally consisting of O, OH, and F. However, recent studies have extended the chemical domain of the surface terminations to other elements, and they should be considered as an additional parameter governing the MXene properties. There is a shortfall in the understanding of how various chemical species could act as terminations on different MXenes. In particular, there is limited comprehension in which chemical environments different terminations are stable. Here, we present an extensive theoretical study of the surface terminations of MXenes in different atmospheres by considering in total six experimentally achieved MXenes (Ti2C, Nb2C, V2C, Mo2C, Ti3C2, and Nb4C3) and twelve surface terminations (O, OH, N, NH, NH2, S, SH, H, F, Cl, Br, and I). We consider fully terminated (single termination) MXenes and also the impact of substituting individual terminations. Our study provides insights into what terminations are stable on which MXenes in different chemical environments, with predictions of how to obtain single-termination MXenes and which MXenes are resilient under ambient conditions. In addition, we propose synthesis protocols of MXenes which have not yet been realized in experiments. It is anticipated that alongside the development of new synthesis routes, our study will provide design rules for how to tailor the surface terminations of MXenes.
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| 17. |
- Blidberg, Andreas, 1987-, et al.
(författare)
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Monitoring LixFeSO4F (x = 1, 0.5, 0) Phase Distributions in Operando To Determine Reaction Homogeneity in Porous Battery Electrodes
- 2017
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Ingår i: Chemistry of Materials. - : American Chemical Society. - 0897-4756 .- 1520-5002. ; 29:17, s. 7159-7169
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Tidskriftsartikel (refereegranskat)abstract
- Increasing the energy and power density simultaneously remains a major challenge for improving electrochemical energy storage devices such as Li-ion batteries. Understanding the underlying processes in operating electrodes is decisive to improve their performance. Here, an extension of an in operando X-ray diffraction technique is presented, wherein monitoring the degree of coexistence between crystalline phases in multiphase systems is used to investigate reaction homogeneity in Li-ion batteries. Thereby, a less complicated experimental setup using commercially available laboratory equipment could be employed. By making use of the intrinsic structural properties of tavorite type LiFeSO4F, a promising cathode material for Li-ion batteries, new insights into its nonequilibrium behavior are gained. Differences in the reaction mechanism upon charge and discharge are shown; the influence of adequate electronic wiring for the cycling stability is demonstrated, and the effect of solid state transport on rate performance is highlighted. The methodology is an alternative and complementary approach to the expensive and demanding techniques commonly employed for time-resolved studies of structural changes in operating battery electrodes. The multiphase behavior of LiFeSO4F is commonly observed for other insertion type electrode materials, making the methodology transferable to other new energy storage materials. By expanding the possibilities for investigating complex processes in operating batteries to a larger community, faster progress in both electrode development and fundamental material research can be realized.
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| 18. |
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| 19. |
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| 20. |
- Brandell, Daniel, et al.
(författare)
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Conduction Mechanisms in Crystalline LiPF6·PEO6 Doped with SiF62- and SF6
- 2005
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Ingår i: Chem. Mater. - : American Chemical Society (ACS). ; 17:14, s. 3673-3680
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Tidskriftsartikel (refereegranskat)abstract
- Molecular dynamics (MD) simulations have been made under imposed electric fields for crystalline LiPF6·PEO6, (LiPF6)1-x(Li2SiF6)x·PEO6, and (LiPF6)1-x(SF6)x·PEO6 for x = 0.01 under standard pressure and temperature conditions with the aim of identifying the conduction mechanisms in the systems. Contrary to the results of earlier experimental investigations where only cation mobility was observed, ionic transport is here found to occur in regions between the polymer hemi-helices, with a high transference number (0.9-1.0) for the PF6- anions.
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| 21. |
- Brant, William, et al.
(författare)
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Selective Control of Composition in Prussian White for Enhanced Material Properties
- 2019
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Ingår i: Chemistry of Materials. - : AMER CHEMICAL SOC. - 0897-4756 .- 1520-5002. ; 31:18, s. 7203-7211
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Tidskriftsartikel (refereegranskat)abstract
- Sodium-ion batteries based on Prussian blue analogues (PBAs) are ideal for large-scale energy storage applications due to the ability to meet the huge volumes and low costs required. For Na2-xFe[Fe(CN)(6)](1-y)center dot zH(2)O, realizing its commercial potential means fine control of the concentration of sodium, Fe(CN)(6) vacancies, and water content. To date, there is a huge variation in the literature of composition leading to variable electrochemical performance. In this work, we break down the synthesis of PBAs into three steps for controlling the sodium, vacancy, and water content via an inexpensive, scalable synthesis method. We produce rhombohedral Prussian white Na1.88(5)Fe[Fe-(CN)(6)]center dot 0.18(9)H2O with an initial capacity of 158 mAh/g retaining 90% capacity after 50 cycles. Subsequent characterization revealed that the increased polarization on the 3 V plateau is coincident with a phase transition and reduced utilization of the high-spin Fe(III)/Fe(II) redox couple. This reveals a clear target for subsequent improvements of the material to boost long-term cycling stability. These results will be of great interest for the myriad of applications of PBAs, such as catalysis, magnetism, electrochromics, and gas sorption.
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| 22. |
- Brorsson, Joakim, 1988, et al.
(författare)
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Order-Disorder Transition in Inorganic Clathrates Controls Electrical Transport Properties
- 2021
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 1520-5002 .- 0897-4756. ; 33:12, s. 4500-4509
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Tidskriftsartikel (refereegranskat)abstract
- Inorganic clathrates have been extensively investigated owing to their unique and intriguing atomic structure as well as their potential as thermoelectric materials. The connection between the chemical ordering and the physical properties has, however, remained elusive. Here, this relation is uncovered through a combination of first-principles calculations, atomistic simulations, and experimental measurements of thermodynamic as well as electrical transport properties. This approach is, specifically, used to reveal the existence of an order-disorder transition in the quaternary clathrate series Ba8AlxGa16-xGe30. The results, furthermore, demonstrate that this phenomenon is responsible for the discontinuity in the heat capacity that has been observed previously. Moreover, the unusual temperature dependence of both Seebeck coefficient and electrical conductivity can be fully explained by the alterations of the band structure brought about by the phase transformation. It is finally argued that the phenomenology described here is not limited to this particular material but should be present in a wide range of inorganic clathrates and could even be observed in other materials that exhibit chemical ordering on at least one sublattice.
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| 23. |
- Bryngelsson, Hanna, et al.
(författare)
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Electrodeposited Sb and Sb/Sb2O3 nanoparticle coatings as anode materials for Li-ion batteries
- 2007
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 19:5, s. 1170-1180
-
Tidskriftsartikel (refereegranskat)abstract
- Galvanostatically electrodeposited coatings of pure Sb or co-deposited Sb and Sb2O3 nanoparticles, prepared from antimony tartrate solutions, were studied as anode materials in Li-ion batteries. It is demonstrated that the co-deposition of 20-25% (w/w) Sb2O3 results from a local pH increase at the cathode (due to protonation of liberated tartrate) in poorly buffered solutions. This causes precipitation of Sb2O3 nanoparticles and inclusion of some of the particles in the deposit where they become coated with a protecting layer of Sb. Chronopotentiometric cycling of the deposits, which also were characterized using, e.g., SEM, TEM, and XRD, clearly showed that the Sb2O3-containing deposits were superior as anode materials. While the Sb/Sb2O3 coatings exhibited a specific capacity close to the Sb theoretical value of 660 mA·h·g -1 during more than 50 cycles, the capacity for the Sb coatings gradually decreased to about 250 mA·h·g-1. This indicates that the influence of the significant volume changes present upon the formation and oxidation of Li3Sb was much smaller for the Sb/Sb2O3 nanoparticle coatings. The improved performance can be explained by significant formation of Sb2O3 during the reoxidation, the presence of smaller Sb particles in the Sb/Sb2O3 coatings, and the formation of buffering nanoparticles of Li2O in a matrix of Sb during the first reduction cycle for the Sb/Sb2O3 deposits.
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| 24. |
- Burbano, M., et al.
(författare)
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Oxygen Vacancy Ordering and the Conductivity Maximum in Y(2)O(3)-Doped CeO(2)
- 2012
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 1520-5002 .- 0897-4756. ; 24:1, s. 222-229
-
Tidskriftsartikel (refereegranskat)abstract
- The defect structure and ionic diffusion processes within the anion-deficient, fluorite structured system Ce(1-x)Y(x)O(2-x/2) have been investigated at high temperatures (873 K-1073 K) as a function of dopant concentration, x, using a combination of neutron diffraction studies, impedance spectroscopy measurements, and molecular dynamics (MD) simulations using interionic potentials developed from ab initio calculations. Particular attention is paid to the short-range ion-ion correlations, with no strong evidence that the anion vacancies prefer, at high temperature, to reside in the vicinity of either cationic species. However, the vacancy-vacancy interactions play a more important role, with preferential ordering of vacancy pairs along the directions, driven by their strong repulsion at closer distances, becoming dominant at high values of x. This effect explains the presence of a maximum in the ionic conductivity in the intermediate temperature range as a function of increasing x. The wider implications of these conclusions for understanding the structure property relationships within anion-deficient fluorite structured oxides are briefly discussed, with reference to complementary studies of yttria and/or scandia doped zirconia published previously.
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| 25. |
- Buscaglia, Maria Teresa, et al.
(författare)
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Fe2O3@BaTiO3 Core−Shell Particles as Reactive Precursors for the Preparation of Multifunctional Composites Containing Different Magnetic Phases
- 2010
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 22:16, s. 4740-4748
-
Tidskriftsartikel (refereegranskat)abstract
- Well-designed reactive precursors and templates allow for careful control of solid-state reactions at the nanoscale level, thus enabling the fabrication of materials with specific microstructures and properties. In this study, Fe2O3@BaTiO3 core−shell particles have been used as precursors for the in situ fabrication of multifunctional composites containing a dielectric/ferroelectric phase and two magnetic phases with contrasting coercivities (Fe2O3/Fe3O4, BaFe12O19/Ba12Fe28Ti15O84). The formation of new magnetic phases occurs during sintering or post-annealing via reaction between BaTiO3 and Fe2O3. The starting powders have been prepared using a multistep process that combines colloidal chemistry methods and a solid-state reaction. The nature and the amount of the magnetic phases and, consequently, the final magnetic properties of the composite can be controlled by varying the relative amount of Fe2O3 (30 or 50 vol %), the densification method (conventional or spark plasma sintering), and the processing temperature. The composites show constricted magnetic hysteresis loops with a coercivity of 0.1−2.5 kOe and a saturation magnetization of 5−16 emu/g. Composites obtained from powders containing 30 vol % Fe2O3 show, at temperatures of 20−80 °C and frequencies between 10 kHz and 1 MHz, a relative dielectric constant of 50 and dielectric losses of <10%.
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| 26. |
- Buscaglia, M. T., et al.
(författare)
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Synthesis of BaTiO3 core-shell particles and fabrication of dielectric ceramics with local graded structure
- 2006
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 18:17, s. 4002-4010
-
Tidskriftsartikel (refereegranskat)abstract
- The coating of BaTiO3 particles with a different perovskite and the subsequent consolidation to dense ceramics retaining a radial composition gradient within the single grains are presented and discussed. A shell of SrTiO3 or BaZrO3 was directly grown on the surface of BaTiO3 spherical templates suspended in aqueous solution by means of a precipitation process making use of inorganic precursors. The overall composition and the particle size can be tailored over a wide range. Densification of the resulting core-shell particles was realized using spark plasma sintering or conventional sintering. Dense ceramics with locally graded structure can be only obtained by a careful choice of the sintering conditions, that is, controlling the interdiffusion between core and shell. The final materials show strongly modified dielectric properties in comparison to both the parent compounds and the homogeneous solid solutions. The proposed approach is generic and suggests a new avenue to create functional and structural polycrystalline materials with locally graded structure by the controlled sintering of core-shell particles.
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| 27. |
- Bykova, Elena, et al.
(författare)
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Novel Class of Rhenium Borides Based on Hexagonal Boron Networks Interconnected by Short B-2 Dumbbells
- 2022
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 34:18, s. 8138-8152
-
Tidskriftsartikel (refereegranskat)abstract
- Transition metal borides are known due to their attractive mechanical, electronic, refractive, and other properties. A new class of rhenium borides was identified by synchrotron single-crystal X-ray diffraction experiments in laser-heated diamond anvil cells between 26 and 75 GPa. Recoverable to ambient conditions, compounds rhenium triboride (ReB3) and rhenium tetraboride (ReB4) consist of close-packed single layers of rhenium atoms alternating with boron networks built from puckered hexagonal layers, which link short bonded (similar to 1.7 angstrom) axially oriented B-2 dumbbells. The short and incompressible Re-B and B-B bonds oriented along the hexagonal c-axis contribute to low axial compressibility comparable with the linear compressibility of diamond. Sub-millimeter samples of ReB3 and ReB4 were synthesized in a large-volume press at pressures as low as 33 GPa and used for material characterization. Crystals of both compounds are metallic and hard (Vickers hardness, H-V = 34(3) GPa). Geometrical, crystal-chemical, and theoretical analysis considerations suggest that potential ReBx compounds with x > 4 can be based on the same principle of structural organization as in ReB3 and ReB4 and possess similar mechanical and electronic properties.
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| 28. |
- Camacho Dejay, Rafael, et al.
(författare)
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Polarization Imaging of Emissive Charge Transfer States in Polymer/Fullerene Blends
- 2014
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 26:23, s. 6695-6704
-
Tidskriftsartikel (refereegranskat)abstract
- Photoexcitation of conjugated polymerfullerene blends results in population of a local charge transfer (CT) state at the interface between the two materials. The competition between recombination and dissociation of this interfacial state limits the generation of fully separated free charges. Therefore, a detailed understanding of the CT states is critical for building a comprehensive picture of the organic solar cells operation. We applied a new fluorescence microscopy method called two-dimensional polarization imaging to gain insight into the orientation of the transition dipole moments of the CT states, and the associated excitation energy transfer processes in TQ1:PCBM blend films. The polymer phase was oriented mechanically to relate the polymer dipole moment orientation to that of the CT states. CT state formation was observed to be much faster than energy transfer in the polymer phase. However, after being formed an emissive CT state does not exchange excitation energy with other CT states, suggesting that they are spatially and/or energetically isolated. We found that the quantum yield of the CT emission is smaller for CT states spatially located in the highly oriented polymer domains, which is interpreted as the result of enhanced CT state dissociation in highly ordered structures.
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| 29. |
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| 30. |
- Charles, Bethan, et al.
(författare)
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Phase Behavior and Substitution Limit of Mixed Cesium-Formamidinium Lead Triiodide Perovskites
- 2020
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 1520-5002 .- 0897-4756. ; 32:6, s. 2282-2291
-
Tidskriftsartikel (refereegranskat)abstract
- The mixed cation lead iodide perovskite photovoltaics show improved stability following site substitution of cesium ions (Cs+) onto the formamidinium cation sites (FA(+)) of (CH(NH2)(2)PbI3 (FAPbI(3)) and increased resistance to formation of the undesirable.-phase. The structural phase behavior of Cs(0.1)FA(0.9)PbI(3) has been investigated by neutron powder diffraction (NPD), complemented by single crystal and power X-ray diffraction and photoluminescence spectroscopy. The Cs-substitution limit has been determined to be less than 15%, and the cubic alpha-phase, Cs(0.1)FA(0.9)PbI(3), is shown to be synthesizable in bulk and stable at 300 K. On cooling the cubic Cs(0.1)FA(0.9)PbI(3), a slow, second-order cubic to tetragonal transition is observed close to 290 K, with variable temperature NPD indicating the presence of the tetragonal beta-phase, adopting the space group P4/mbm between 290 and 180 K. An orthorhombic phase or twinned tetragonal phase is formed below 180 K, and the temperature for further transition to a disordered state is lowered to 125 K compared to that seen in phase pure alpha-FAPbI(3) (140 K). These results demonstrate the importance of understanding the effect of cation site substitution on structure-property relationships in perovskite materials.
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| 31. |
- Charrier, Dimitri S. H., et al.
(författare)
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Large Electrically Induced Height and Volume Changes in Poly(3,4-ethylenedioxythiophene)/Poly(styrenesulfonate) Thin Films
- 2010
-
Ingår i: Chemistry of Materials. - : American Chemical Society. - 0897-4756 .- 1520-5002. ; 22:12, s. 3670-3677
-
Tidskriftsartikel (refereegranskat)abstract
- We demonstrate large, partly reversible height and volume changes of thin films of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) on the anode of interdigitating gold electrodes under ambient conditions by applying an electrical bias. The height and volume changes were monitored with optical and atomic force microscopy and are found to be independent of initial film thickness. In the first cycle, a relative height change of 950% is observed for a 21 nm thick film. Two regimes are identified. In the first regime, reversible redox reactions occur and reversible height changes can be ascribed to absorption of water via osmotic effects, brought about by an increasing ion concentration on the anode. In the second, irreversible regime, irreversible overoxidation of the PEDOT occurs and mass transport from the channel to the anode becomes important.
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| 32. |
- Chen, Hong, et al.
(författare)
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3D Open-Framework Vanadoborate as a Highly Effective Heterogeneous Pre-catalyst for the Oxidation of Alkylbenzenes
- 2013
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 25:24, s. 5031-5036
-
Tidskriftsartikel (refereegranskat)abstract
- Three three-dimensional (3D) open-framework vanadoborates, denoted as SUT-6-Zn, SUT-6-Mn, and SUT-6-Ni, were synthesized using diethylenetriamine as a template. SUT-6-Zn, SUT-6-Mn, and SUT-6-Ni are isostructural and built from (VO)(12)O-6 B18O36(OH)(6) clusters bridged by ZnO5, MnO6, and NiO6 polyhedra, respectively, to form the 3D frameworks. SUT-6 is the first vanadoborate with a 3D framework. The framework follows a semiregular hxg net topology with a 2-fold interpenetrated diamond-like channel system. The amount of template used in the synthesis played an important role in the dimensionality of the resulting vanadoborate structures. A small amount of diethylenetriamine led to the formation of this first 3D vanadoborate framework, while an increased amount of diethylenetriamine resulted in vanadoborates with zero-dimensional (0D) and one-dimensional (1D) structures. SUT-6-Zn was proved to be an efficient heterogeneous precatalyst for the oxidation of alkylbenzenes.
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| 33. |
- Chen, Ruikui, et al.
(författare)
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Effect of tetrahydroquinoline dyes structure on the performance of organic dye-sensitized solar cells
- 2007
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 19:16, s. 4007-4015
-
Tidskriftsartikel (refereegranskat)abstract
- Eleven novel donor acceptor pi-conjugated (D-pi-A) organic dyes have been engineered and synthesized as sensitizers for the application in dye-sensitized solar cells (DSSCs). The electron-donating moieties are substituted tetrahydroquinoline, and the electron-withdrawing parts are cyanoacrylic acid group or cyanovinylphosphonic acid group. Different lengths of thiophene-containing conjugation moieties (thienyl, thienylvinyl, and dithieno[3,2-b;2',3'-d]thienyl) are introduced to the molecules and serve as electron spacers. Detailed investigation on the relationship between the dye structure, photophysical and photoelectrochemical properties, and performance of DSSCs is described here. The bathochromic shift and increase of the molar extinction coefficient of the absorption spectrum are achieved by introduction of larger conjugation moiety. Even small structural changes of dyes result in significant changes in redox energies and adsorption manner of the dyes on TiO2 surface, affecting dramatically the performance of DSSCs based on these dyes. The higher performances are obtained by DSSCs based on the rigid dye molecules, C2 series dyes (Figure 1), although these dyes have lower light absorption abilities relative to other dyes. A maximum solar-to-electrical energy conversion efficiency (eta) of 4.53% is achieved under simulated AM 1.5 irradiation (100 mW/cm(2)) with a DSSC based on C2-2 dye (V-oc = 597 mV, J(sc) = 12.00 mA/cm(2), ff = 0.63). Density functional theory (DFT) calculations have been performed on the dyes, and the results show that electron distribution from the whole molecules to the anchoring moieties occurred during the HOMO-LUMO excitation. The cyanoacrylic acid groups or cyanovinylphosphonic acid group are essentially coplanar with respect to the thiophene units, reflecting the strong conjugation across the thiophene-anchoring groups.
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| 34. |
- Chen, Yaqi, et al.
(författare)
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Insight into the Extreme Side Reaction between LiNi0.5Co0.2Mn0.3O2 and Li1.3Al0.3Ti1.7(PO4)3 during Cosintering for All-Solid-State Batteries
- 2023
-
Ingår i: Chemistry of Materials. - 1520-5002 .- 0897-4756. ; 35:22, s. 9647-9656
-
Tidskriftsartikel (refereegranskat)abstract
- All-solid-sate batteries (ASSBs) with a NASICON-type solid-state electrolyte (SSE) of Li1.3Al0.3Ti1.7(PO4)3 (LATP) can be accepted as a promising candidate to significantly improve safety and energy density due to their high oxidation potential and high ionic conductivity. However, thermodynamic instability between the cathode and LATP is scarcely investigated during cosintering preparation for the integrated configuration of ASSBs. Herein, the structural compatibility between commercially layered LiNi0.5Co0.2Mn0.3O2 (NCM523) and LATP SSE was systematically investigated by cosintering at 600 °C. It is noticeable that an extreme side reaction between Li from NCM523 and phosphate from LATP happens during its cosintering process, leading to a severe phase transition from a layered to a spinel structure with high Li/Ni mixing. Consequently, the capacity of NCM523 is lost during the preparation of the NCM523-LATP composite cathode. Based on this, we suggested that the interface modification of the NCM523/LATP interface is valued significantly to inhibit this extreme side reaction, quickening the application of LATP-based ASSBs.
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| 35. |
- Cheng, Ming, et al.
(författare)
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Highly Efficient Integrated Perovskite Solar Cells Containing a Small Molecule-PC70BM Bulk Heterojunction Layer with an Extended Photovoltaic Response Up to 900 nm
- 2016
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 28:23, s. 8631-8639
-
Tidskriftsartikel (refereegranskat)abstract
- We demonstrate a high efficiency perovskite solar cell (PSC) integrated with a bulk heterojunction layer, based on acceptor-donor-acceptor (A-D-A) type hole transport material (HTM) and PC70BM composite, yielding improved photoresponse. Two A-D-A-structured hole transporting materials termed M3 and M4 were designed and synthesized. Applied as HTMs in PSCs, power conversion efficiencies (PCEs) of 14.8% and 12.3% were obtained with M3 and M4, respectively. The HTMs M3 and M4 show competitive absorption, but do not contribute to photocurrent, resulting in low current density. This issue was solved by mixing the HTMs with PC70BM to form a bulk heterojunction (BHJ) layer and integrating this layer into the PSC as hole transport layer (HTL). Through careful interface optimization, the (FAPbI(3))(0.85)(MAPbBr(3))(0.15)/HTM:PC70BM integrated devices showed improved efficiencies of 16.2% and 15.0%, respectively. More importantly, the incident-photon-to-current conversion efficiency (IPCE) spectrum shows that the photoresponse is extended to 900 nm by integrating the M4:PC70BM based BHJ and (FAPbI(3))(0.85)(MAPbBr(3))(0.15) layers.
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| 36. |
- Cheng, Ming, et al.
(författare)
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Novel Small Molecular Materials Based on Phenoxazine Core Unit for Efficient Bulk Heterojunction Organic Solar Cells and Perovskite Solar Cells
- 2015
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 27:5, s. 1808-1814
-
Tidskriftsartikel (refereegranskat)abstract
- Two novel Acceptor-Donor-Acceptor (A-D-A) structured small molecular (SM-) materials POZ2 and POZ3 using an electron-rich phenoxazine (POZ) unit as a core building block were designed and synthesized. Their unique characteristics, such as suitable energy levels, strong optical absorption in the visible region, high hole mobility, and high conductivity, prompted us to use them both as p-type donor materials (DMs) in SM-bulk heterojunction organic solar cells (BHJ OSCs) and as hole transport materials (HTMs) in CH3NH3PbI3-based perovskite solar cells (PSCs). The POZ(2)-based devices yielded promising power conversion efficiencies (PCEs) of 7.44% and 12.8% in BHJ OSCs and PSCs, respectively, which were higher than the PCEs of 6.73% (BHJ-OSCs) and 11.5% (PSCs) obtained with the POZ3-based devices. Moreover, our results demonstrated that the POZ2 employing the electron-deficient benzothiazole (BTZ) as linker exhibited higher hole mobility and conductivity than that of the POZ3 using thiophene as linker, leading to better device performance both in BHJ-OSCs and PSCs. These results also provide guidance for the molecular design of high charge carrier mobility SM-materials for highly efficient BHJ OSCs and PSCs in the future.
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| 37. |
- Chi, X, et al.
(författare)
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Structure and transport properties of the charge-transfer salt coronene - TCNQ
- 2004
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 16:26, s. 5751-5755
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Tidskriftsartikel (refereegranskat)abstract
- Coronene is a highly symmetric organic molecule whose molecular structure resembles a fragment of graphite. We have crystallized a charge-transfer complex based on coronene and TCNQ, and present crystal structure and transport properties. The complex adopts alternate stacking between coronene and TCNQ and the charge-transfer was estimated to be of the order of 0.3 by the structure and IR analysis of TCNQ. This degree of charge-transfer is larger than those of other hydrocarbon based charge-transfer complexes reported. We find semiconductor behavior with an optical gap of 1.55 eV and a transport gap of 0.49 eV. The Child's law mobility is estimated to be 0.3 cm(2)/Vs-this alone, with the small tran-sport gap suggests this compound might be attractive for device applications.
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| 38. |
- Cho, Jung, et al.
(författare)
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EMM-25 : The Structure of Two-Dimensional 11 x 10 Medium-Pore Borosilicate Zeolite Unraveled Using 3D Electron Diffraction
- 2021
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 33:11, s. 4146-4153
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Tidskriftsartikel (refereegranskat)abstract
- The structure of the novel medium-pore borosilicate zeolite EMM-25 has been determined by continuous rotation electron diffraction (cRED). EMM-25 crystallizes in the space group Cmcm with unit cell parameters a = 11.055, b = 22.912, and c = 24.914 angstrom and a composition of IC4H8(C11H25N)(2)I (2)[Si112.5B3.5O232]. The EMM-25 framework possesses a two-dimensional channel system composed of 10-ring channels connected via 11-ring windows. Its channel system is analogous to that of the medium-pore zeolite NU-87 framework but with 11- rather than 12-ring windows, suggesting a different shape selectivity. EMM-25 was first obtained using 1,4-bis(N-methyl-N,N-dihexylammonium)butane as an organic structure directing agent (OSDA). Based on a molecular docking study of the OSDA within the pores of the determined framework structure, a new ammonium dication OSDA with an improved fit was devised. By using this new OSDA, the synthesis time was reduced 80%, from 52 to just 10 days. Furthermore, cRED data revealed a structural disorder of the EMM-25 framework present as swinging zigzag chains. The introduction of the disorder, which is a consequence of geometry relaxation, was crucial for an accurate structure refinement. Lastly, the cRED data from as-made EMM-25 showed residual potential consistent with the location of the OSDA position determined from the Rietveld refinement, concluding a complete refinement of the as-made structure based on the cRED data.
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| 39. |
- Chubarov, Mikhail, et al.
(författare)
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Polytype pure sp2-BN thin films as dictated by the substrate crystal structure
- 2015
-
Ingår i: Chemistry of Materials. - Washington : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 27:5, s. 1640-1645
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Tidskriftsartikel (refereegranskat)abstract
- Boron nitride (BN) is a promising semiconductor material, but its current exploration is hampered by difficulties in growth of single crystalline phase-pure thin films. We compare the growth of sp2-BN by chemical vapor deposition on (0001) 6H-SiC and on (0001) α-Al2O3 substrates with an AlN buffer layer. Polytype-pure rhombohedral BN (r-BN) with a thickness of 200 nm is observed on SiC whereas hexagonal BN (h-BN) nucleates and grows on the AlN buffer layer. For the latter case after a thickness of 4 nm, the h-BN growth is followed by r-BN growth to a total thickness of 200 nm. We find that the polytype of the sp2-BN films is determined by the ordering of Si-C or Al-N atomic pairs in the underlying crystalline structure (SiC or AlN). In the latter case the change from h-BN to r-BN is triggered by stress relaxation. This is important for the development of BN semiconductor device technology.
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| 40. |
- Corma, Averlino, et al.
(författare)
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Synthesis and structure of polymorph B of zeolite Beta
- 2008
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 20:9, s. 3218-3223
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Tidskriftsartikel (refereegranskat)abstract
- It was found that either polymorph B or polymorph C of zeolite beta can be obtained from the same structure directing agent: 4,4-dimethyl-4-azonia-tricyclo[5.2.2.02,6]undec-8-ene hydroxide. The synthesis occurs through a consecutive process where polymorph B is first formed and then transformed into polymorph C. It is possible to produce a zeolite highly enriched in polymorph B, provided that the transformation of this phase into polymorph C is slowed down up to the point where polymorph C is only detected at trace levels. The structure of polymorph B was determined for the first time by electron crystallography with SAED and HRTEM from areas of unfaulted polymorph B crystals.
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| 41. |
- Crispin, Xavier, 1972-, et al.
(författare)
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The origin of the high conductivity of poly(3,4-ethylenedioxythiophene)- poly(styrenesulfonate) (PEDOT-PSS) plastic electrodes
- 2006
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 18:18, s. 4354-4360
-
Tidskriftsartikel (refereegranskat)abstract
- The development of printed and flexible (opto)electronics requires specific materials for the device's electrodes. Those materials must satisfy a combination of properties. They must be electrically conducting, transparent, printable, and flexible. The conducting polymer poly(3,4-ethylenedioxythiophene) - poly-(styrenesulfonate) (PEDOT-PSS) is known as a promising candidate. Its conductivity can be increased by 3 orders of magnitude by the secondary dopant diethylene glycol (DEG). This "secondary doping" phenomenon is clarified in a combined photoelectron spectroscopy and scanning probe microscopy investigation. PEDOT-PSS appears to form a three-dimensional conducting network explaining the improvement of its electrical property upon addition of DEG. Polymer light emitting diodes are successfully fabricated using the transparent plastic PEDOT-PSS electrodes instead of the traditionally used indium tin oxide. © 2006 American Chemical Society.
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| 42. |
- Crowley, T.A., et al.
(författare)
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Synthesis of metal and metal oxide nanowires and nanotube arrays within a mesoporous silica template
- 2003
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 15:18, s. 3518-3522
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Tidskriftsartikel (refereegranskat)abstract
- Metallic nanowires of cobalt, copper, and iron oxide magnetite (Fe3O4) have been synthesized within the pores of mesoporous silica using a supercritical fluid inclusion technique. The mesoporous matrix provides a means of producing a high density of stable, hexagonally ordered arrays of highly crystalline nanowires. The formation of the metal and metal oxide nanowires within the silica mesopores was confirmed by transmission electron microscopy (TEM), N2 adsorption experiments, and powder X-ray diffraction (PXRD). The mechanism of nanowire formation within the mesopores appears to occur through the initial binding and coating of the pore walls with the metal atoms to form tubelike structures within the mesoporous template. The thickness of these tubes subsequently increases with further metal deposition until nanowires are formed. Additionally, the crystal structure of the cobalt nanowires formed within the mesoporous template can be readily changed by manipulating the density of the supercritical fluid phase.
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| 43. |
- D'acunto, Giulio, et al.
(författare)
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Bimolecular Reaction Mechanism in the Amido Complex-Based Atomic Layer Deposition of HfO2
- 2023
-
Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 35:2, s. 529-538
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Tidskriftsartikel (refereegranskat)abstract
- The surface chemistry of the initial growth during the first or first few precursor cycles in atomic layer deposition is decisive for how the growth proceeds later on and thus for the quality of the thin films grown. Yet, although general schemes of the surface chemistry of atomic layer deposition have been developed for many processes and precursors, in many cases, knowledge of this surface chemistry remains far from complete. For the particular case of HfO2 atomic layer deposition on a SiO2 surface from an alkylamido-hafnium precursor and water, we address this lack by carrying out an operando atomic layer deposition experiment during the first cycle of atomic layer deposition. Ambient-pressure X-ray photoelectron spectroscopy and density functional theory together show that the decomposition of the metal precursor on the stoichiometric SiO2 surface in the first half-cycle of atomic layer deposition proceeds via a bimolecular reaction mechanism. The reaction leads to the formation of Hf-bonded methyl methylene imine and free dimethylamine. In addition, ligand exchange takes place involving the surface hydroxyls adsorbed at defect sites of the SiO2 surface.
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| 44. |
- Davydova, Alexandra, et al.
(författare)
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The Single Phase Region in Cu2ZnSnS4 Thin Films from Theory and Combinatorial Experiments
- 2018
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 30:14, s. 4624-4638
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Tidskriftsartikel (refereegranskat)abstract
- Cu2ZnSnS4 (CZTS) is hoped to be a future, earth-abundant absorber material for thin film solar cells, but performance remains below the level needed for commercialization. In this work, the size of the single phase region of CZTS obtained from thin film synthesis methods is explored, to determine the scope available for defect engineering and thereby future improvements in solar cell performance. A chemical model for the single phase region is presented, based on equilibria between defect complexes in the CZTS phase and the other solid- and gas-phase components present during synthesis. The model predicts a variable single phase region size, depending on the partial pressures of SnS and S2. The model is verified by analysis of combinatorial thin-film CZTS samples prepared with different synthetic conditions and characterized by Raman and compositional mapping. We conclude that typical synthesis strategies for CZTS are not capable of accessing the full range of the CZTS single phase region since the required partial pressure of S2 is very large. The important implication is that our understanding of CZTS defect chemistry from experimental studies is incomplete and that scope exists for tuning the defect properties toward better solar cell performance.
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| 45. |
- De Toro, José A., et al.
(författare)
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Remanence Plots as a Probe of Spin Disorder in Magnetic Nanoparticles
- 2017
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Ingår i: Chemistry of Materials. - Washington, D.C., USA : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 29:19, s. 8258-8268
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Tidskriftsartikel (refereegranskat)abstract
- Remanence magnetization plots (e.g., Henkel or delta M plots) have been extensively used as a straightforward way to determine the presence and intensity of dipolar and exchange interactions in assemblies of magnetic nanoparticles or single domain grains. Their evaluation is particularly important in functional materials whose performance is strongly affected by the intensity of interparticle interactions, such as patterned recording media and nanostructured permanent magnets, as well as in applications such as hyperthermia and magnetic resonance imaging. Here, we demonstrate that delta M plots may be misleading when the nanoparticles do not have a homogeneous internal magnetic configuration. Substantial dips in the delta M plots of gamma-Fe2O3 nanoparticles isolated by thick SiO2 shells indicate the presence of demagnetizing interactions, usually identified as dipolar interactions. results, however, demonstrate that it is the inhomogeneous spin structure of the nanoparticles, as most clearly evidenced by Mossbauer measurements, that has a pronounced effect on the delta M plots, leading to features remarkably similar to those produced by dipolar interactions. X-ray diffraction results combined with magnetic characterization indicate that this inhomogeneity is due to the presence of surface structural (and spin) disorder. Monte Carlo simulations unambiguously corroborate the critical role of the internal magnetic structure in the delta M plots. Our findings constitute a cautionary tale on the widespread use of remanence plots to assess interparticle interactions as well as offer new perspectives in the use of Henkel and delta M plots to quantify the rather elusive inhomogeneous magnetization states in nanoparticles.
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| 46. |
- Doherty, Walter J, et al.
(författare)
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Conducting polymer growth in porous sol-gel thin films : Formation of nanoelectrode arrays and mediated electron transfer to sequestered macromolecules
- 2005
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 17:14, s. 3652-3660
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Tidskriftsartikel (refereegranskat)abstract
- The templated electrochemical growth of poly(3,4-ethylenedioxythiophene) (PEDOT) into porous sol-gel (PSG) films and PEDOT-mediated electron transfer to ferrocene-modified dendrimers encapsulated within these sol-gel matrices, were analyzed. The conditions needed to optimize PEDOT electropolymerization within the PSG films such that barely emergent PEDOT features protrude from a PSG thin film surface, were also described. It was observed that oxidation/reduction of the encapsulated Fc-PAMAM units could be voltammetrically detected after PEDOT growth into the sol-gel film. The results show that up to ca. 20% of these Fc-PAMAM units became electrochemically active, with high rates of electron transfer, when EDTM was conjugated to the Fc-PAMAM dendrimer.
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| 47. |
- Dombrovskis, Johanna, 1986, et al.
(författare)
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Transition Metal Ion-Chelating Ordered Mesoporous Carbons as Noble Metal-Free Fuel Cell Catalysts
- 2013
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 1520-5002 .- 0897-4756. ; 25:6, s. 856-861
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Tidskriftsartikel (refereegranskat)abstract
- A new concept for noble metal-free polymer electrolyte membrane fuel cell catalysts has been developed. The catalysts consist of chelated transition metal ions incorporated in a nitrogen-functionalized ordered mesoporous carbon matrix, which is evidenced by a combination of X-ray absorption fine structure analysis and high-resolution transmission electron microscopy. The ordered mesoporous carbon matrix of the catalyst offers an exceptionally high specific surface area and allows conceptually for a high degree of tuning, enabling controlled variability of, e.g., pore size and curvature and thickness of the pore walls of the catalysts. Single cell fuel cell tests of membrane electrode assemblies prepared with a cathode made of iron- or cobalt-based versions of the catalyst show high power densities, reaching up to one-third of a commercial Pt/C catalyst at 0.6 V.
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| 48. |
- Doverbratt, Isa, et al.
(författare)
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Linear Metal Chains in Ca2M2X (M = Pd, Pt; X = Al, Ge): Origin of the Pairwise Distortion and Its Role in the Structure Stability
- 2015
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 27:1, s. 304-315
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Tidskriftsartikel (refereegranskat)abstract
- A series of four new analogue phases Ca2M2X (M = Pd, Pt and X = Al, Ge) were prepared by direct combination of the respective elements in stoichiometric mixtures at high temperature in order to analyze the impact of valence electron count (vec) and electronegativity differences (Delta chi) on the structure selection and stability. Their crystal structures, as determined from single-crystal X-ray diffraction data, correspond to two different but closely related structure types. The first compound, Ca2Pd2Ge (I), is an unprecedented ternary ordered variant of the Zr2Al3-type (orthorhombic, Fdd2). The three other phases, Ca2Pt2Ge (II), Ca2Pd2Al (III) and Ca2Pt2Al (IV), adopt the Gd2Ge2Al-type structure (monoclinic, C-2/c). All title structures feature linear chains of the noble metals (Pd or Pt). The Pd linear chains in I are undistorted with equidistant Pd center dot center dot center dot Pd atoms, whereas the metal chains in II-IV are pairwise distorted, resulting in short connected {Pd-2} or {Pt-2} dumbbells that are separated by longer M center dot center dot center dot M contacts. The occurrence and magnitude of the pairing distortion in these chains are controlled by the vec and the Delta chi between the constituent elements, a result which is supported by analysis of the calculated Bader effective charges. The metal chains act as charge modulation units, critical for the stability and the electronic flexibility of the structures by an adequate adjustment of the metal-metal bond order to both the vec and the degree of charge transfer. Thus, Ca2Pd2Ge (28 ve/f.u) is a Zintl-like, charge optimized phase with formally zerovalent Pd atoms forming the undistorted metal chains; semimetallic properties are predicted by TB-LMTO calculations. In contrast, the isoelectronic Ca2Pt2Ge is predicted to be a good metal with the Fermi level located at a local maximum of the DOS, a fingerprint of potential electronic instability. This is due to greater charge transfer to the more electronegative Pt atoms forming the metal chains and probably to packing frustration in the well packed structure that may prevent a larger distortion of the Pt chains. However, the instability is suppressed in the aliovalent but isostructural phases Ca2M2Al (27 ve/f.u) with an enhancement of the pairing distortion within the metal chains but lower M-M bond order. Further reduction of the vec as in Ca2M2Cd (26 ve/f.u) may induce a transition toward the more geometrically flexible W2CoB2-type with a low dimensional structure, to create more room for a larger distortion of the metal chain as dictated by the shortage of valence electrons.
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| 49. |
- Drvarič Talian, Sara, et al.
(författare)
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Fluorinated Ether Based Electrolyte for High-Energy Lithium-Sulfur Batteries: Li+ Solvation Role behind Reduced Polysulfide Solubility
- 2017
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 1520-5002 .- 0897-4756. ; 29:23, s. 10037-10044
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Tidskriftsartikel (refereegranskat)abstract
- By employing new electrolytes, the polysulfide shuttle phenomenon, one of the main problems of lithium-sulfur (Li-S) batteries, can be significantly reduced. Here we present excellent Coulombic efficiencies as well as adequate performance of high-energy Li-S cells by the use of a fluorinated ether (TFEE) based electrolyte at low electrolyte loading. The observed altered discharge profile was investigated both by electrochemical experiments and an especially tailored COSMO-RS computational approach, while the details of the discharge mechanism were elucidated by two operando techniques: XANES and UV-vis spectroscopy. A significant decrease of polysulfide solubility compared to tetraglyme is due to different Li+ solvation mode.
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| 50. |
- Duarte, T. A. G., et al.
(författare)
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A Glance at Novel Ionanofluids Incorporating Silk-Derived Carbon Dots
- 2024
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 36:3, s. 1136-1152
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Tidskriftsartikel (refereegranskat)abstract
- One of the hallmarks of the current efforts in the field of thermal energy is heat transfer enhancement. Ionanofluids (INFs), a combination of nanomaterials and ionic liquids (ILs), are an appealing category of thermal fluids. In this work, we introduce sustainable INFs composed of carbon dots derived from Bombyx mori silk fibroin (SF) dispersed in a mixture of 1-butyl-3-methylimidazolium chloride (IL1) and 1-(4-sulfobutyl)-3-methylimidazolium triflate (IL2). The syntheses were performed at mild conditions, with reaction times of 3, 4, and 5 h, and without purification steps. The INFs display room-temperature emission in the visible spectral range with quantum yield values up to 0.09 and are essentially viscous fluids (G″ > G′). A marked shear thinning behavior is observed at high shear rates, particularly for the systems SFIL1IL2-3h and SFIL1IL2-4h. The INFs demonstrate relatively high heat capacity and thermal conductivity values in comparison to state-of-the-art INFs. Under suitable illumination conditions, the INFs can convert light into heat in an efficient manner, with photothermal conversion efficiencies of up to 28%, similar to other reported INFs. SFIL1IL2-5h exhibits remarkable stability over time within the range of working temperatures. This work paves the way for the development of new thermal fluids for enhanced heat transfer technologies using sustainable synthesis routes and natural raw precursor materials.
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