Sign reversal of the mixed-state Hall resistivity in type-II superconductors

Taking into account pinning, thermal fluctuations, and vortex-vortex interactions, we develop a unified theory to explain the sign reversal of the mixed-state Hall resistivity ρ xy in both high-T c and low-T c superconductors. Molecular dynamics simulations show that besides the pinning forces, either the thermal fluctuations in the high-T c superconductors or the vortex-vortex interactions in the low-T c ones play an important role in the sign reversal of ρ xy. From a calculated phase diagram for vortex motion, we find that the abnormal Hall effect always occurs in the plastic flow state of vortices. ©1999 The American Physical Society.published_or_final_versio

Switching effective oxygen reduction and evolution performance by controlled graphitization of a cobalt-nitrogen-carbon framework system

We report a purposely designed route for the synthesis of a promising carbon-based electrocatalyst for both ORR (oxygen reduction reaction) and OER (oxygen evolution reaction) from zeolitic imidazolate frameworks (ZIFs). Firstly, precursor ZIFs are rationally designed with a blend of volatile zinc to induce porosity and stable cobalt to induce graphitic domains. Secondly, the self-modulated cobalt–nitrogen–carbon system (SCNCS) is shown to be an effective ORR catalyst after graphitization at mild temperatures. Finally, the best OER catalyst is developed by enhancing graphitization of the SCNCS. For the first time, solely by switching the graphitization conditions of SCNCS, excellent ORR or OER performance is realized. This approach not only opens up a simple protocol for simultaneous optimization of nitrogen doping and graphitization at controlled cobalt concentrations, but also provide a facile method of developing such active catalysts without the use of extensive synthesis procedures

Relative edge energy in the stability of transition metal nanoclusters of different motifs

When a structure is reduced to a nanometer scale, the proportion of the lowly-coordinated edge atoms increases significantly, which can play a crucial role in determining both their geometric and electronic properties, as demonstrated by the recently established generalized Wulff construction principle [S. F. Li, et al., Phys. Rev. Lett., 2013, 111, 115501]. Consequently, it is of great interest to clarify quantitatively the role of the edge atoms that dominate the motifs of these nanostructures. In principle, establishing an effective method valid for determining the absolute value of the surface energy and particularly the edge energy for a given nanostructure is expected to resolve such a problem. However, hitherto, it is difficult to obtain the absolute edge energy of transition metal clusters, particularly when their sizes approach the nanometer regime. In this paper, taking Ru nanoclusters as a prototypical example, our first-principles calculations introduce the concept of relative edge energy (REE), reflecting the net edge atom effect over the surface (facet) atom effect, which is fairly powerful to quasi-quantitatively estimate the critical size at which the crossover occurs between different configurations of a given motif, such as from an icosahedron to an fcc nanocrystal. By contrast, the bulk effect should be re-considered to rationalize the power of the REE in predicting the relative stability of larger nanostructures between different motifs, such as fcc-like and hcp-like nanocrystals

Substrate co-doping modulates electronic metal-support interactions and significantly enhances single-atom catalysis

Transitional metal nanoparticles or atoms deposited on appropriate substrates can lead to highly economical, efficient, and selective catalysis. One of the greatest challenges is to control the electronic metal–support interactions (EMSI) between the supported metal atoms and the substrate so as to optimize their catalytic performance. Here, from first-principles calculations, we show that an otherwise inactive Pd single adatom on TiO2(110) can be tuned into a highly effective catalyst, e.g. for O2 adsorption and CO oxidation, by purposefully selected metal–nonmetal co-dopant pairs in the substrate. Such an effect is proved here to result unambiguously from a significantly enhanced EMSI. A nearly linear correlation is noted between the strength of the EMSI and the activation of the adsorbed O2 molecule, as well as the energy barrier for CO oxidation. Particularly, the enhanced EMSI shifts the frontier orbital of the deposited Pd atom upward and largely enhances the hybridization and charge transfer between the O2 molecule and the Pd atom. Upon co-doping, the activation barrier for CO oxidation on the Pd monomer is also reduced to a level comparable to that on the Pd dimer which was experimentally reported to be highly efficient for CO oxidation. The present findings provide new insights into the understanding of the EMSI in heterogeneous catalysis and can open new avenues to design and fabricate cost-effective single-atom-sized and/or nanometer-sized catalysts

Co3+-O-V4+ cluster in CoVOx nanorods for efficient and stable electrochemical oxygen evolution

The development of cost-efficient and long-term stable catalysts for the oxygen evolution reaction (OER) is crucial to produce clean and sustainable H2 fuels from water. Here we demonstrate a cobalt vanadium oxide (CoVOx-300) working as such an efficient and durable electrocatalyst. Such an active catalyst is beneficial from the balanced Co3+-O-V4+ active species, which show the high surface Co3+ contents with matched V4+ generated by rapid heat treatment. The CoVOx-300 with highest Co3+/Co2+ ratio of 1.4 and corresponding highest V4+/ V5+ ratio of 1.7 exhibits remarkable OER activity with an overpotential of 330 mV at current density of 10 mA cm−2 (η10), a shallow Tafel slope of only 46 mV dec-1 and a current density of 100 mA cm−2 at an overpotential of 0.38 V vs RHE, which is 20 times higher than the active CoOx-300 and 1000 times higher than VOx-300. The catalyst also shows excellent stability for 10 h in alkaline media and a 40 % reduced activation energy to the counterpart, CoOx-300. The overpotential (η10) of CoVOx-300 also shows nearly 70 and 80 mV lower than the corresponding CoOx-300 and CoVOx catalysts, respectively and 20 % lower Tafel slope than the commercial benchmark catalyst RuO2. Thus, this study for the first time demonstrates that surface Co3+-O-V4+ species play a crucial role in improving electrocatalytic properties and stability for water oxidation reaction and the approaches allow the rational design and synthesis of other active transition metal oxides toward efficient OER activity

Supercapacitor and supercapattery as emerging electrochemical energy stores

This article reviews critically selected recent literature on electrochemical energy storage (EES) technologies, focusing on supercapacitor and also supercapattery which is a generic term for various hybrid devices combining the merits of rechargeable battery and supercapacitor. Fundamentals of EES are explained, aiming at clarification of some literature confusions such as the differences between capacitive and non-capacitive Faradaic charge storage mechanisms, and between cathode and positive electrode (positrode), and between anode and negative electrode (negatrode). In particular, the concept and origin of pseudocapacitance are qualitatively correlated with the band model for semiconductors. Strategies for design and construction of supercapattery are discussed in terms of both the materials structures and device engineering. Selection of materials, including electrolytes, is another topic reviewed selectively. Graphenes and carbon nanotubes are the favourable choice to composite with both capacitive and non-capacitive redox materials for improved kinetics of charge storage processes and charge-discharge cycling stability. Organoaqueous electrolytes show a great potential to enable EES to work at sub-zero temperatures, whilst solid ion conducting membranes and ionic liquids can help develop high voltage (> 4.0 V) and hence high energy supercapatteries

Phylogeographic analysis and genetic structure of an endemic sino-japanese disjunctive genus Diabelia (caprifoliaceae)

The Sino-Japanese Floristic Region (SJFR) is a key area for plant phylogeographical research, due to its very high species diversity and disjunct distributions of a large number of species and genera. At present, the root cause and temporal origin of the discontinuous distribution of many plants in the Sino-Japanese flora are still unclear. Diabelia (Caprifoliaceae; Linnaeoideae) is a genus endemic to Asia, mostly in Japan, but two recent discoveries in China raised questions over the role of the East China Sea (ECS) in these species' disjunctions. Chloroplast DNA sequence data were generated from 402 population samples for two regions (rpl32-trnL, and trnH-psbA) and 11 nuclear microsatellite loci were screened for 549 individuals. Haplotype, population-level structure, combined analyses of ecological niche modeling, and reconstruction of ancestral state in phylogenies were also performed. During the Last Glacial Maximum (LGM) period after the Tertiary, Diabelia was potentially widely distributed in southeastern China, the continental shelf of the East China Sea and Japan (excluding Hokkaido). After LGM, all populations in China have disappeared except those in Zhejiang which may represent a Glacial refuge. Populations of Diabelia in Japan have not experienced significant bottleneck effects, and populations have maintained a relatively stable state. The observed discontinuous distribution of Diabelia species between China and Japan are interpreted as the result of relatively ancient divergence. The phylogenetic tree of chloroplast fragments shows the characteristics of multi-origin evolution (except for D. sanguinea). STRUCTURE analysis of nuclear Simple Sequence Repeat (nSSR) showed that the plants of the Diabelia were divided into five gene pools: D. serrata, D. spathulata, D. sanguinea, D. ionostachya (D. spathulata var. spathulata-Korea), and populations of D. ionostachya var. ionostachya in Yamagata prefecture, northern Japan. Molecular evidence provides new insights of Diabelia into biogeography, a potential glacial refuge, and population-level genetic structure within species. In the process of species differentiation, ECS acts as a corridor for two-way migration of animals and plants between China and Japan during glacial maxima, providing the possibility of secondary contact for discontinuously distributed species between China and Japan, or as a filter (creating isolation) during glacial minima. The influence of the ECS in speciation and biogeography of Diabelia in the Tertiary remains unresolved in this study. Understanding origins, evolutionary histories, and speciation will provide a framework for the conservation and cultivation of Diabelia

An oxidized magnetic Au single atom on doped TiO2(110) becomes a high performance CO oxidation catalyst due to the charge effect

Catalysis using gold nanoparticles supported on oxides has been under extensive investigation for many important application processes. However, how to tune the charge state of a given Au species to perform a specific chemical reaction, e.g. CO oxidation, remains elusive. Here, using first-principles calculations, we show clearly that an intrinsically inert Au anion deposited on oxygen-deficient TiO2(110) (Au@TiO2(110)) can be tuned and optimized into a highly effective single atom catalyst (SAC), due to the depletion of the d-orbital by substrate doping. Particularly, Ni- and Cu-doped Au@TiO2 complexes undergo a reconstruction driven by one of the two dissociated O atoms upon CO oxidation. The remaining O atom heals the surface oxygen vacancy and results in a stable bow-shaped surface “O–Au–O” species; thereby the highly oxidized Au single atom now exhibits magnetism and dramatically enhanced activity and stability for O2 activation and CO oxidation, due to the emergence of high density of states near the Fermi level. Based on further extensive calculations, we establish the “charge selection rule” for O2 activation and CO oxidation on Au: the positively charged Au SAC is more active than its negatively charged counterpart for O2 activation, and the more positively charged the Au, the more active it is

Graphene Inclusion Induced Ultralow Thermal Conductivity and Improved Figure of Merit in p-type SnSe

The concept of composite material has been increasingly applied for the significant improvement on the thermoelectric performance because of the predictable effective medium properties and the unique interfacial correlated thermal...</p