| 1. |
- Liang, Lin, et al.
(författare)
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Non-Interpenetrated Single-Crystal Covalent Organic Frameworks
- 2020
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 59:41, s. 17991-17995
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Tidskriftsartikel (refereegranskat)abstract
- Growth of covalent organic frameworks (COFs) as single crystals is extremely challenging. Inaccessibility of open-structured single-crystal COFs prevents the exploration of structure-oriented applications. Herein we report for the first time a non-interpenetrated single-crystal COF, LZU-306, which possesses the open structure constructed exclusively via covalent assembly. With a high void volume of 80 %, LZU-306 was applied to investigate the intrinsic dynamics of reticulated tetraphenylethylene (TPE) as the individual aggregation-induced-emission moiety. Solid-state(2)H NMR investigation has determined that the rotation of benzene rings in TPE, being the freest among the reported cases, is as fast as 1.0x10(4) Hz at 203 K to 1.5x10(7) Hz at 293 K. This research not only explores a new paradigm for single-crystal growth of open frameworks, but also provides a unique matrix-isolation platform to reticulate functional moieties into a well-defined and isolated state.
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| 2. |
- Xu, Hai-Sen, et al.
(författare)
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Single crystal of a one-dimensional metallo-covalent organic framework
- 2020
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 11:1
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Tidskriftsartikel (refereegranskat)abstract
- Although polymers have been studied for well over a century, there are few examples of covalently linked polymer crystals synthesised directly from solution. One-dimensional (1D) covalent polymers that are packed into a framework structure can be viewed as a 1D covalent organic framework (COF), but making a single crystal of this has been elusive. Herein, by combining labile metal coordination and dynamic covalent chemistry, we discover a strategy to synthesise single-crystal metallo-COFs under solvothermal conditions. The single-crystal structure is rigorously solved using single-crystal electron diffraction technique. The non-centrosymmetric metallo-COF allows second harmonic generation. Due to the presence of syntactic pendant amine groups along the polymer chains, the metallopolymer crystal can be further cross-linked into a crystalline woven network. Although polymers have been studied for well over a century, there are few examples of covalently linked polymer crystals synthesized directly from solution. Here, the authors demonstrate a strategy to synthesize single crystalline 1D metallo-covalent organic frameworks by combining dynamic covalent chemistry and metal-ligand coordination.
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| 3. |
- Lin, Ke, et al.
(författare)
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Identification of Free OH and its Implication on Structural Changes of Liquid Water
- 2013
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Ingår i: Chinese Journal of Chemical Physics. - : AIP Publishing. - 1674-0068 .- 2327-2244. ; 26:2, s. 121-126
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Tidskriftsartikel (refereegranskat)abstract
- The molecular structure of liquid water has been an outstanding issue for many years. The identification of free -OH holds the key in differentiating structure models for liquid water. By analyzing the relative changes of the intensity and depolarization ratio in temperature dependent Raman spectra, the occurrence of free -OH in liquid water is unambiguously determined. Furthermore, upon the increase of temperature from 5 degrees C to 85 degrees C, the structure of liquid water undergoes significant change, but the relative proportion of free -OH is considerably small and remains almost unchanged. This implies that the breaking of hydrogen bond from the tetrahedral structure prefers to occur at the site of the hydrogen acceptor. The energetic favoring of the structural change for liquid water is thus clearly revealed from experiments.
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| 4. |
- Lin, Ke, et al.
(författare)
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Quantum Effects on Global Structure of Liquid Water
- 2013
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Ingår i: Chinese Journal of Chemical Physics. - : AIP Publishing. - 1674-0068 .- 2327-2244. ; 26:2, s. 127-132
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Tidskriftsartikel (refereegranskat)abstract
- The structure difference between light and heavy liquid water has been systematically investigated by high precision Raman. spectroscopy over the temperature range of 5-85 degrees C. Distinct difference between the Raman spectral profiles of two different liquid waters is clearly observed. By analyzing the temperature-dependent Raman spectral contour using global fitting procedure, it is found that the micro-structure of heavy water is more ordered than that of light water at the same temperature, and the structure difference between the light and heavy water decreases with the increase of the temperature. The temperature offset, an indicator for the structure difference, is determined to vary from 28 degrees C to 18 degrees C for the low-to-high temperature. It indicates that quantum effect is significantly not only at low temperature, but also at room temperature. The interaction energy among water molecules has also been estimated from van't Hoff's relationship. The detailed structural information should help to develop reliable force fields for molecular modeling of liquid water.
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| 5. |
- Tian, Gui-Xian, et al.
(författare)
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Facile Hydrothermal Synthesis of Highly Efficient and Durable Ternary PtPdCu Electrocatalysts for the Methanol Oxidation Reaction
- 2023
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Ingår i: Advanced Energy & Sustainability Research. - : Wiley. - 2699-9412.
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Tidskriftsartikel (refereegranskat)abstract
- Precious metal Pt-based electrocatalysts have been widely used in the methanol catalytic oxidation anodes in direct methanol fuel cells. However, decreasing their cost and improving their efficiency and durability have still been challenging. Herein, ternary PtPdCu nanocatalysts are synthesized through a facile one-step hydrothermal synthesis method. When KI is present with a suitable amount in the synthesis, PtPdCu nanospheres with surface-embedded CuI clusters (CuI/PtPdCu) are fabricated. However, without KI, the prepared PtPdCu catalysts show a distinct hollow structure (h-PtPtCu). CuI/PtPdCu displays the highest specific activity with enhancement 4 times higher than commercial Pt/C for the methanol oxidation reaction in an alkaline medium. The superior activity can be attributed to two aspects: 1) the electronic effect originating from the highly alloyed PtPdCu; 2) the synergetic effect resulting from surface inlaid CuI clusters, which can promote the CO intermediate removal. Furthermore, because of the stable Pt-Pd-rich surface and its special linked hollow structure, the h-PtPtCu catalyst exhibits good durability with only a 3.6% decay in the specific activity.
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| 6. |
- Yang, Yi, et al.
(författare)
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Facile Hydrothermal Synthesis of Highly Efficient and Durable Ternary Ptpdcu Electrocatalysts For Methanol Oxidation Reaction : Iodide Matters
- 2022
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Ingår i: Social Science Research Network SSRN. - : Elsevier BV. - 1556-5068.
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Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- Precious metal Pt-based electrocatalysts have been widely used in methanol catalytic oxidation of anodes in direct methanol fuel cells (DMFCs). However, it has been still the challenge to decrease their cost and improve their efficiency and stability. In this study, ternary PtPdCu nanocatalysts were synthesized through a facile one-step hydrothermal synthesis method. When KI was present with a suitable amount in the synthesis, PtPdCu nanospheres with surface embedded CuI clusters (CuI/PtPdCu) were obtained. While without using KI, the prepared PtPdCu catalysts show a distinct hollow structure (h-PtPtCu). CuI/PtPdCu displays the highest specific activity with a 4 times enhancement than commercial Pt/C for methanol oxidation reaction (MOR) in an alkaline medium. The superior activity can attribute to the two aspects: i) Electronic effect originated from the highly alloyed PtPdCu. ii) synergetic effect due to the surface inlayed CuI clusters which can promote the CO intermediate removal. Furthermore, owing to the stable Pt-Pd-rich surface and its special linked hollow structure, h-PtPtCu catalyst exhibits the best durability with only a 3.6 % decay in specific activity.
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| 7. |
- Diller, Katharina, et al.
(författare)
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Polyphenylsilole multilayers - an insight from X-ray electron spectroscopy and density functional theory
- 2015
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 17:46, s. 31117-31124
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Tidskriftsartikel (refereegranskat)abstract
- We present a combined investigation by means of X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy of condensed multilayers of two polyphenylsiloles, namely hexaphenylsilole (HPS) and tetraphenylsilole (TPS). Both compounds exhibit very similar spectroscopic signatures, whose interpretation is aided by density functional theory (DFT) calculations. High-resolution XPS spectra of the Si 2p and C 1s core levels of these multilayers indicate a positively charged silicon ion flanked by two negatively charged adjacent carbon atoms in the silole core of both molecules. This result is corroborated quantitatively by DFT calculations on isolated HPS (TPS) molecules, which show a natural bond orbital partial charge of + 1.67 e (+1.58 e) on the silicon and -0.34 e (-0.58 e) on the two neighbouring carbon atoms in the silole ring. These charges are conserved in direct contact with a Cu(111) substrate for films of submonolayer coverage, as evidenced by the Si 2p XPS data. The C K-edge NEXAFS spectra of HPS and TPS multilayers exhibit distinct and differing features. Their main characteristics reappear in the simulated spectra and are assigned to the different inequivalent carbon species in the molecule. The angle-dependent measurements hardly reveal any dichroism, i.e., the molecular p-systems are not uniformly oriented parallel or perpendicular with respect to the surface. Changes in the growth conditions of TPS, i.e., a reduction of the substrate temperature from 240 K to 80 K during deposition, lead to a broadening of both XPS and NEXAFS signatures, as well as an upward shift of the Si 2p and C 1s binding energies, indicative of a less ordered growth mode at low temperature.
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| 8. |
- Fang, Qiu, et al.
(författare)
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Photodissociation of phosgene : Theoretical evidence for the ultrafast and synchronous concerted three-body process
- 2009
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 131:16
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Tidskriftsartikel (refereegranskat)abstract
- The potential energy surfaces for Cl2CO dissociation into CO+Cl+Cl in the lowest two electronic singlet states (S-0 and S-1) have been determined by the complete active space self-consistent field, coupled-cluster method with single and double excitations (CCSD), and equation-of-motion CCSD calculations, which are followed by direct ab initio molecular dynamics simulations to explore its photodissociation dynamics at 230 nm. It is found that the C-O stretching mode is initially excited upon irradiation and the excess internal energies are transferred to the C-Cl symmetric stretching mode within 200 fs. On average, the first and the second C-Cl bonds break completely within subsequent 60 and 100 fs, respectively. Electronic structure and dynamics calculations have thus provided a strong evidence that the photoinitiated dissociation of Cl2CO at 230 nm or shorter wavelengths is an ultrafast, adiabatic, and concerted three-body process. Since the two C-Cl bonds begin to break at the same time and the time interval between the two C-Cl bond broken fully is very short (similar to 40 fs), the photoinitiated dissociation of Cl2CO to CO+2Cl can be considered as the synchronous concerted process.
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| 9. |
- Hu, Wei, et al.
(författare)
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Vibrational identification for conformations of trans-1,2-bis (4-pyridyl) ethylene in gold molecular junctions
- 2015
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Ingår i: Chemical Physics. - : Elsevier BV. - 0301-0104 .- 1873-4421. ; 453-454, s. 20-25
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Tidskriftsartikel (refereegranskat)abstract
- The surface-enhanced Raman scattering (SERS) spectroscopy and inelastic electron tunneling spectroscopy (IETS) are employed to study trans-1,2-bis (4-pyridyl) ethylene (BPE)/gold system. Both junction and complex forms are considered for the SERS simulations. It is predicted that the peak at 1581 cm-1 is more intense in the junction forms than that in the complex forms. Time dependent density functional theory calculations show that the relative intensity is mainly controlled by the excitation energy derivative respect to the normal modes, and the total intensity is governed by the excitation energy of the excited states. The CH bending modes dominate the IET spectra when BPE adsorbed on the flat gold surfaces. While, the pyridyl ring deformation modes are more active when BPE adsorbed on the edge of the gold clusters. For BPE adsorbed on the tip of gold clusters, the pyridyl ring and CC stretching modes show significant contribution to the IET spectra.
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| 10. |
- Kapilashrami, Mukes, et al.
(författare)
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Understanding the magnetic interaction between intrinsic defects and impurity ions in room-temperature ferromagnetic Mg1-xFexO thin films
- 2016
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Ingår i: Journal of Physics. - : IOP Publishing. - 0953-8984 .- 1361-648X. ; 28:15
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Tidskriftsartikel (refereegranskat)abstract
- Understanding the nature and characteristics of the intrinsic defects and impurities in the dielectric barrier separating the ferromagnetic electrodes in a magnetic tunneling junction is of great importance for understanding the often observed 'barrier-breakdown' therein. In this connection, we present herein systematic experimental (SQUID and synchrotron-radiation-based x-ray absorption spectroscopy) and computational studies on the electronic and magnetic properties of Mg1-xFexO thin films. Our studies reveal: (i) defect aggregates comprised of basic and trimer units (Fe impurity coupled to 1 or 2 Mg vacancies) and (ii) existence of two competing magnetic orders, defect- and dopant-induced, with spin densities aligning anti-parallel if the trimer is present in the oxide matrix. These findings open up new avenues for designing tunneling barriers with high endurance and tunneling effect upon tuning the concentration/distribution of the two magnetic orders.
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