| 1. |
- Pang, Kanglei, 1993-, et al.
(författare)
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Redirecting configuration of atomically dispersed selenium catalytic sites for efficient hydrazine oxidation
- 2024
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Ingår i: Matter. - 2590-2393 .- 2590-2385. ; 7:2, s. 655-667
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Tidskriftsartikel (refereegranskat)abstract
- Understanding the reconstruction of surface sites is crucial for gaining insights into the true active sites and catalytic mechanisms. While extensive research has been conducted on reconstruction behaviors of atomically dispersed metallic catalytic sites, limited attention has been paid to non-metallic ones despite their potential catalytic activity comparable or even superior to their noble-metal counterpart. Herein, we report a carbonaceous, atomically dispersed non-metallic selenium catalyst that displayed exceptional catalytic activity in the hydrazine oxidation reaction (HzOR) in alkaline media, outperforming the noble-metal Pt catalysts. In situ X-ray absorption spectroscopy (XAS) and Fourier transform infrared spectroscopy revealed that the pristine SeC4 site pre-adsorbs an ∗OH ligand, followed by HzOR occurring on the other side of the OH–SeC4. Theoretical calculations proposed that the pre-adsorbed ∗OH group pulls electrons from the Se site, resulting in a more positively charged Se and a higher polarity of Se–C bonds, thereby enhancing surface reactivity toward HzO/R.
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| 2. |
- Wang, Binmin, et al.
(författare)
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Multifunctional Underwater Adhesive Film Enabled by a Single-Component Poly(ionic liquid)
- 2023
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Ingår i: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 17:6, s. 5871-5879
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Tidskriftsartikel (refereegranskat)abstract
- Tremendous efforts have been devoted to exploiting synthetic wet adhesives for real-life applications. However, developing low-cost, robust, and multifunctional wet adhesive materials remains a considerable challenge. Herein, a wet adhesive composed of a single-component poly(ionic liquid) (PIL) that enables fast and robust underwater adhesion is reported. The PIL adhesive film possesses excellent stretchability and flexibility, enabling its anchoring on target substrates regardless of deformation and water scouring. Surface force measurements show the PIL can achieve a maximum adhesion of 56.7 mN·m–1 on diverse substrates (both hydrophilic and hydrophobic substrates) in aqueous media, within ∼30 s after being applied. The adhesion mechanisms of the PIL were revealed via the force measurements, and its robust wet adhesive capacity was ascribed to the synergy of different non-covalent interactions, such as of hydrogen bonding, cation−π, electrostatic, and van der Waals interactions. Surprisingly, this PIL adhesive film exhibited impressive underwater sound absorption capacity. The absorption coefficient of a 0.7 mm-thick PIL film to 4–30 kHz sound waves could be as high as 0.80–0.92. This work reports a multifunctional PIL wet adhesive that has promising applications in many areas and provides deep insights into interfacial interaction mechanisms underlying the wet adhesion capability of PILs.
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| 3. |
- Shao, Yue, et al.
(författare)
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Scalable Synthesis of Photoluminescent Single-Chain Nanoparticles by Electrostatic-Mediated Intramolecular Crosslinking
- 2022
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 61:27
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Tidskriftsartikel (refereegranskat)abstract
- We report the large-scale synthesis of photoluminescent single-chain nanoparticles (SCNPs) by electrostatic-mediated intramolecular crosslinking in a concentrated solution of 40 mg mL−1 by continuous addition of the free radical initiator. Poly(vinyl benzyl chloride) was charged by quaternization with vinyl-imidazolium for the intramolecular crosslinking by using 2,2-dimethoxy-2-phenylacetophenone (DMAP) as the radical initiator. Under the electrostatic repulsion thus interchain isolation, the intrachain crosslinking experiences the transition from coil through pearl-necklace to globular state. The SCNPs demonstrate strong photoluminescence in the visible range when the non-emissive units are confined thereby. Composition and microstructure of the SCNPs are tunable. The photoluminescent tadpole-like Janus SCNP can be used to selectively illuminate interfacial membranes while stabilizing the emulsions.
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| 4. |
- Zhai, Xiaohu, et al.
(författare)
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Roles of Anion–Cation Coupling Transport and Dehydration-Induced Ion–Membrane Interaction in Precise Separation of Ions by Nanofiltration Membranes
- 2022
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 56:19, s. 14069-14079
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Tidskriftsartikel (refereegranskat)abstract
- Nanofiltration (NF) membranes are playing increasingly crucial roles in addressing emerging environmental challenges by precise separation, yet understanding of the selective transport mechanism is still limited. In this work, the underlying mechanisms governing precise selectivity of the polyamide NF membrane were elucidated using a series of monovalent cations with minor hydrated radius difference. The observed selectivity of a single cation was neither correlated with the hydrated radius nor hydration energy, which could not be explained by the widely accepted NF model or ion dehydration theory. Herein, we employed an Arrhenius approach combined with Monte Carlo simulation to unravel that the transmembrane process of the cation would be dominated by its pairing anion, if the anion has a greater transmembrane energy barrier, due to the constraint of anion–cation coupling transport. Molecular dynamics simulations further revealed that the distinct hydration structure was the primary origin of the energy barrier difference of cations. The cation having a larger incompressible structure after partial dehydration through subnanopores would induce a more significant ion–membrane interaction and consequently a higher energy barrier. Moreover, to validate our proposed mechanisms, a membrane grafting modification toward enlarging the energy barrier difference of dominant ions achieved a 3-fold enhancement in ion separation efficiency. Our work provides insights into the precise separation of ionic species by NF membranes.
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| 5. |
- Bin, Li, et al.
(författare)
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Self-Assembly of Miktoarm Star Polyelectrolytes in Solutions with Various Ionic Strengths
- 2022
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Ingår i: ACS Omega. - : American Chemical Society (ACS). - 2470-1343. ; 7:24, s. 20791-20799
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Tidskriftsartikel (refereegranskat)abstract
- We studied the self-assembly of miktoarm star polyelectrolytes with different numbers of arms in solutions with various ionic strengths using coarse-grained molecular dynamic simulations. Spherical micelles are obtained for star polyelectrolytes with fewer arms, whereas wormlike clusters are obtained for star polyelectrolytes with more arms at a low ionic strength environment, with hydrophilic arms showing a stretched conformation. The number of clusters shows an overall decreasing tendency with increasing the number of arms in star polyelectrolytes due to strong electrostatic coupling between polycations and polyanions. The formation of wormlike clusters follows an overall stepwise pathway with an intermittent association–dissociation process for star polyelectrolytes with weak electrostatic coupling. These computational results can provide relevant physical insights to understand the self-assembly mechanism of star polyelectrolytes in solvents with various ionic strengths and to design star polyelectrolytes with functional groups that can fine-tune self-assembled structures for specific applications.
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| 6. |
- Khan, Inayat Ali, et al.
(författare)
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Effect of structural variation in biomass-derived nonfluorinated ionic liquids electrolytes on the performance of supercapacitors
- 2022
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Ingår i: Journal of Energy Chemistry. - : Elsevier. - 2095-4956 .- 2096-885X. ; 69, s. 174-184
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Tidskriftsartikel (refereegranskat)abstract
- There is a growing interest in sustainable and high performance supercapacitors (SCs) operating at elevated temperatures as they are highly demanded in heat-durable electronics. Here, we present a biomass-derived nonfluorinated ionic liquid (IL) [P4444][HFuA] and its structural analogue [P4444][TpA] as electrolytes for supercapacitors comprising multiwall carbon nanotubes and activated charcoal (MWCNTs/AC) mixed carbon composite electrodes. A detailed investigation of the effect of scan rate, temperature, potential window and orientation of ions on the electrodes surfaces is performed. The supercapacitors exhibited relatively lower specific capacitance for both [P4444][HFuA] and [P4444][TpA] ILs at room temperature. However, the specific capacitance has significantly increased with an increase in temperature and potential window. The equivalent serie resistances of the SCs is deceased with increasing temperatures, which is a result of improved ionic conductivities of the IL electrolytes. In CV cycling at 60 °C, the capacitor with [P4444][HFuA] IL-based electrolyte retained about 90% of its initial capacitance, while the capacitor with [P4444][TpA] IL-based electrolyte retained about 83% of its initial capacitance. Atomistic computations revealed that the aromatic [FuA]− and [TpA]− anions displayed perpendicular distribution that can effectively neutralize charges on the carbon surfaces. However, the [HFuA]− anion exhibited somewhat tilted configurations on the carbon electrode surfaces, contributing to their outstanding capacitive performance in electrochemical devices.
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| 7. |
- Li, Xinghao, et al.
(författare)
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Porous organic polycarbene nanotrap for efficient and selective gold stripping from electronic waste
- 2023
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 14
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Tidskriftsartikel (refereegranskat)abstract
- The role of N-heterocyclic carbene, a well-known reactive site, in chemical catalysis has long been studied. However, its unique binding and electron-donating properties have barely been explored in other research areas, such as metal capture. Herein, we report the design and preparation of a poly(ionic liquid)-derived porous organic polycarbene adsorbent with superior gold-capturing capability. With carbene sites in the porous network as the “nanotrap”, it exhibits an ultrahigh gold recovery capacity of 2.09 g/g. In-depth exploration of a complex metal ion environment in an electronic waste-extraction solution indicates that the polycarbene adsorbent possesses a significant gold recovery efficiency of 99.8%. X-ray photoelectron spectroscopy along with nuclear magnetic resonance spectroscopy reveals that the high performance of the polycarbene adsorbent results from the formation of robust metal-carbene bonds plus the ability to reduce nearby gold ions into nanoparticles. Density functional theory calculations indicate that energetically favourable multinuclear Au binding enhances adsorption as clusters. Life cycle assessment and cost analysis indicate that the synthesis of polycarbene adsorbents has potential for application in industrial-scale productions. These results reveal the potential to apply carbene chemistry to materials science and highlight porous organic polycarbene as a promising new material for precious metal recovery.
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| 8. |
- Liu, Mingren, et al.
(författare)
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Ion Bridging by Carbon Dioxide Facilitates Electrochemical Energy Storage at Charged Carbon–Ionic–Liquid Interfaces
- 2023
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Ingår i: Advanced Energy Materials. - 1614-6832 .- 1614-6840. ; 13:21
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Tidskriftsartikel (refereegranskat)abstract
- Solvent free ionic liquid (IL) electrolytes facilitate high-voltage supercapacitors with enhanced energy density, but their complex ion arrangement and through that the electrochemical properties, are limited by strong Coulombic ordering in the bulk state and like-charged ion repulsion at electrified interfaces. Herein, a unique interfacial phenomenon resulting from the presence of carbon dioxide loaded in 1-Ethyl-3-methylimidazoliumtetrafluorborate electrolyte that simultaneously couples to IL ions and nitrogen-doped carbonaceous electrode is reported. The adsorbed CO2 molecule polarizes and mitigates the electrostatic repulsion among like-charged ions near the electrified interface, leading to an ion “bridge effect” with increased interfacial ionic density and significantly enhanced charge storage capability. The unpolarized CO2 possessing a large quadrupole moment further reduces ion coupling, resulting in higher conductivity of the bulk IL and improved rate capability of the supercapacitor. This work demonstrates polarization-controlled like-charge attraction at IL–electrode–gas three-phase boundaries, providing insights into manipulating complex interfacial ion ordering with small polar molecule mediators.
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| 9. |
- Wang, Yong-Lei, 1983-
(författare)
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Electrostatic Interactions in Coarse-Grained Simulations : Implementations and Applications
- 2013
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Electrostatic interactions between charged species play a prominent role in determining structures and states of physical system, leading to important technological and biological applications. In coarse-grained simulations, accurate description of electrostatic interactions is crucial in addressing physical phenomena at larger spatial and longer temporal scales.In this thesis, we implement ENUF method, an abbreviation for Ewald summation based on non-uniform fast Fourier transform technique, into dissipative particle dynamics (DPD) scheme. With determined suitable parameters, the computational complexity of ENUF-DPD method is approximately described as O(N logN). The ENUF-DPD method is further validated by investigating dependence of polyelectrolyte conformations on charge fraction of polyelectrolyte and counterion valency of added salts, and studying of specific binding structures of dendrimers on amphiphilic membranes.In coarse-grained simulations, electrostatic interactions are either explicitly calculated with suitable methods, or implicitly included in effective potentials. The effect of treatment fashion of electrostatic interactions on phase behavior of [BMIM][PF6] ionic liquid (IL) is systematically investigated. Our systematic analyses show that electrostatic interactions should be incorporated explicitly in development of effective potentials, as well as in coarse-grained simulations to improve reliability of simulation results.Detailed image of microscopic structures and orientations of [BMIM][PF6] at graphene and vacuum interfaces are investigated by using atomistic simulations. Imidazolium rings and alkyl side chains of [BMIM] lie preferentially flat on graphene surface. At IL-vacuum interface, ionic groups pack closely together to form polar domains, leaving alkyl side chains populated at interface and imparting hydrophobic character. With the increase of IL filmthickness, orientations of [BMIM] change gradually from dominant flat distributions along graphene surface to orientations where imidazolium rings are either parallel or perpendicular to IL-vacuum interface with tilted angles. The interfacial spatial ionic structural heterogeneity formed by ionic groups also contributes to heterogeneous dynamics in interfacial regions.
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| 10. |
- Wang, Yong-Lei, 1983-, et al.
(författare)
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Implementation of non-uniform FFT based Ewald summation in dissipative particle dynamics method
- 2013
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Ingår i: Journal of Computational Physics. - : Elsevier BV. - 0021-9991 .- 1090-2716. ; 235, s. 666-682
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Tidskriftsartikel (refereegranskat)abstract
- The ENUF method, i.e., Ewald summation based on the non-uniform FFT technique (NFFT), is implemented in dissipative particle dynamics (DPD) simulation scheme to fast and accurately calculate the electrostatic interactions at mesoscopic level. In a simple model electrolyte system, the suitable ENUF–DPD parameters, including the convergence parameter α, the NFFT approximation parameter p, and the cut-offs for real and reciprocal space contributions, are carefully determined. With these optimized parameters, the ENUF–DPD method shows excellent efficiency and scales as O(NlogN)O(NlogN). The ENUF–DPD method is further validated by investigating the effects of charge fraction of polyelectrolyte, ionic strength and counterion valency of added salts on polyelectrolyte conformations. The simulations in this paper, together with a separately published work of dendrimer–membrane complexes, show that the ENUF–DPD method is very robust and can be used to study charged complex systems at mesoscopic level.
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