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1.
The use of single-atom metals (SAM) as catalysts of energy conversion reactions is a recent topic, which has gained popularity in the last two decades. Transition metal dichalcogenides emerged as important electrocatalysts since it was discovered that their chalcogenide edge sites are active towards the electrocatalytic hydrogen evolution reaction (HER) and could also serve as supports for other metals within the same applications. Currently, several groups have reported a novel metal?chalcogenide arrangement, with the possibility of isolating metals at specific sites on chalcogenides to enhance their properties resulting in a synergistic effect in which both chalcogenide and single-atom metal features are exploited, either as promoters or active sites. Theoretical studies have been the basis of these reports.  相似文献   
2.
Micromechanical deformation phenomena such as those leading to macroscopic viscoelastic and plastic behavior must be studied from a thermodynamic viewpoint, as they induce complex and partly irreversible heat effects. Calorimetric measurements of the intrinsic volumetric thermomechanical heat sources (THS) activated in the material bulk during mechanical loads can produce valuable information with respect to that aim. They can be based on infrared imaging if submitted to inverse algorithms that allow a correct reconstruction of THS to be produced. Here, an inverse method relying on a diffusion-advection heat transfer model is applied to experimental temperature maps recorded during tensile tests. These are made on a semi-crystalline polymer that shows a strong development of plastic instabilities. Along with simultaneous kinematic observables produced with a digital image correlation system, the competition between advection and diffusion phenomena may be clearly established. 1-D profiles of the reconstructed THS and measured strain rates illustrate clearly that thermomechanical effects associated with necking onset and propagation follow the kinematic variable in a rather direct manner. Finally, we show for tensile experiments that THS estimations lead to analyze plasticity as a rheological behavior controlled by the flow stress, responsible of necking development and propagation.  相似文献   
3.
A batch Markov arrival process (BMAP) X* = (N, J) is a 2-dimensional Markov process with two components, one is the counting process N and the other one is the phase process J. It is proved that the phase process is a time-homogeneous Markov chain with a finite state-space, or for short, Markov chain. In this paper, a new and inverse problem is proposed firstly: given a Markov chain J, can we deploy a process N such that the 2-dimensional process X* = (N, J) is a BMAP? The process X* = (N, J) is said to be an adjoining BMAP for the Markov chain J. For a given Markov chain the adjoining processes exist and they are not unique. Two kinds of adjoining BMAPs have been constructed. One is the BMAPs with fixed constant batches, the other one is the BMAPs with independent and identically distributed (i.i.d) random batches. The method we used in this paper is not the usual matrix-analytic method of studying BMAP, it is a path-analytic method. We constructed directly sample paths of adjoining BMAPs. The expressions of characteristic (D k , k = 0, 1, 2 · · ·) and transition probabilities of the adjoining BMAP are obtained by the density matrix Q of the given Markov chain J. Moreover, we obtained two frontal Theorems. We present these expressions in the first time.  相似文献   
4.
The combination of supramolecular chemistry and soft colloids as microgels represents an ambitious way to develop multi-versatile colloidal assemblies. Hereafter, terpyridine-functionalized poly(N-isopropylacrylamide) (PNiPAM) microgel building blocks are shown to undergo an assemble–freeze–disassemble process. The microgel assemblies, which are controlled by monitoring the attractive and repulsive potentials between the soft colloidal particles, are then frozen by forming inter-particle metal–terpyridine bis-complexes upon addition of the metallic cation (such as FeII, CoII). By oxidation of the metal–terpyridine bis-complex links, the aggregates open up, which is due to the complex dissociation releasing the connected particles in the form of single microgels. We extended our work to the development of 1D filaments and 2D membranes materials made of soft particles connected via supramolecular chemistry.  相似文献   
5.
Studies on N2 activation and transformation by transition metal hydride complexes are of particular interest and importance. The synthesis and diverse transformations of a dinitrogen dititanium hydride complex bearing the rigid acridane-based acriPNP-pincer ligands {[(acriPNP)Ti]2(μ2-η1:η2-N2)(μ2-H)2} are presented. This complex enabled N2 cleavage and hydrogenation even without additional H2 or other reducing agents. Furthermore, diverse transformations of the N2 unit with a variety of organometallic compounds such as ZnMe2, MgMe2, AlMe3, B(C6F5)3, PinBH, and PhSiH3 have been well established at the rigid acriPNP-ligated dititanium framework, such as reversible bonding-mode change between the end-on and side-on/end-on fashions, diborylative N=N bond cleavage, the formal insertion of two dimethylaluminum species into the N=N bond, and the formal insertion of two silylene units into the N=N bond. This work has revealed many unprecedented aspects of dinitrogen reaction chemistry.  相似文献   
6.
A multi‐state and multi‐stimuli‐responsive oxazine molecular switch that combines an electro‐base property and sensitive base/acid‐responsive properties was designed and synthesized. The multi‐state structures of the molecular switch, with different colors, were predicted by comparing the optical properties with reference molecules and confirmed by using NMR spectroscopy. The color‐switching mechanism under stimulation with acids and bases was investigated by using DFT calculations. Three single states can be obtained and the switching is unidirectional under acid and base stimulation. The electrochromic phenomenon of the molecular switch, which combines its electro‐base and base‐sensitive properties, was demonstrated. An electrochromic device that exhibited good electrochromic properties with excellent reversibility (2000 cycles) and high coloration efficiency (804 cm2 C?1) was successfully constructed.  相似文献   
7.
本文合成了三种具有多氢键的联萘酚轴手性硫脲催化剂,并将其用于催化合成1,4-二氢吡啶衍生物。结果显示,所合成的新型多氢键硫脲均表现出较好的催化作用,能有效地提高1,4-二氢吡啶衍生物的收率和对映选择性。所有新化合物结构均经过~1H NMR、~(13)C NMR、IR、熔点等表征所确认。  相似文献   
8.
Necessary and sufficient conditions for qualitative properties of infinite dimensional linear programing problems such as solvability, duality, and complementary slackness conditions are studied in this article. As illustrations for the results, we investigate the parametric version of Gale’s example.  相似文献   
9.
10.
The ever‐increasing demand for rechargeable batteries induces significant pressure on the worldwide metal supply, depleting resources and increasing costs and environmental concerns. In this context, developing the chemistry of anion‐inserting electrode organic materials could promote the fabrication of molecular (metal‐free) rechargeable batteries. However, few examples have been reported because little effort has been made to develop such anionic‐ion batteries. Here we show the design of two anionic host electrode materials based on the N‐substituted salts of azaaromatics (zwitterions). A combination of NMR, EDS, FTIR spectroscopies coupled with thermal analyses and single‐crystal XRD allowed a thorough structural and chemical characterization of the compounds. Thanks to a reversible electrochemical activity located at an average potential of 2.2 V vs. Li+/Li, the coupling with dilithium 2,5‐(dianilino)terephthalate (Li2DAnT) as the positive electrode enabled the fabrication of the first all‐organic anionic rechargeable batteries based on crystallized host electrode materials capable of delivering a specific capacity of ≈27 mAh/gelectrodes with a stable cycling over dozens of cycles (≈24 Wh/kgelectrodes).  相似文献   
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