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

Flexible and Accurate Simulation of Radiation Cooling with FETD Method

Thermal management and simulation are becoming increasingly important in many areas of engineering applications. There are three cooling routes for thermal management, namely thermal conduction, thermal convection and thermal radiation, among which the first two approaches have been widely studied and applied, while the radiation cooling has not yet attracted much attention in terrestrial environment because it usually contributes less to the total amount of thermal dissipation. Thus the simulation method for radiation cooling was also seldom noticed. The traditional way to simulate the radiation cooling is to solve the thermal conduction equation with an approximate radiation boundary condition, which neglects the wavelength and angular dependence of the emissivity of the object surface. In this paper, we combine the heat conduction equation with a rigorous radiation boundary condition discretized by the finite-element time-domain method to simulate the radiation cooling accurately and flexibly. Numerical results are given to demonstrate the accuracy, flexibilities and potential applications of the proposed method. The proposed numerical model can provide a powerful tool to gain deep physical insight and optimize the physical design of radiation cooling

Interface Coupling in Twisted Multilayer Graphene by Resonant Raman Spectroscopy of Layer Breathing Modes.

Raman spectroscopy is the prime nondestructive characterization tool for graphene and related layered materials. The shear (C) and layer breathing modes (LBMs) are due to relative motions of the planes, either perpendicular or parallel to their normal. This allows one to directly probe the interlayer interactions in multilayer samples. Graphene and other two-dimensional (2d) crystals can be combined to form various hybrids and heterostructures, creating materials on demand with properties determined by the interlayer interaction. This is the case even for a single material, where multilayer stacks with different relative orientations have different optical and electronic properties. In twisted multilayer graphene there is a significant enhancement of the C modes due to resonance with new optically allowed electronic transitions, determined by the relative orientation of the layers. Here we show that this applies also to the LBMs, which can be now directly measured at room temperature. We find that twisting has a small effect on LBMs, quite different from the case of the C modes. This implies that the periodicity mismatch between two twisted layers mostly affects shear interactions. Our work shows that ultralow-frequency Raman spectroscopy is an ideal tool to uncover the interface coupling of 2d hybrids and heterostructures

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

Phylogeography of the South China Field Mouse (Apodemus draco) on the Southeastern Tibetan Plateau Reveals High Genetic Diversity and Glacial Refugia

The southeastern margin of the Tibetan Plateau (SEMTP) is a particularly interesting region due to its topographic complexity and unique geologic history, but phylogeographic studies that focus on this region are rare. In this study, we investigated the phylogeography of the South China field mouse, Apodemus draco, in order to assess the role of geologic and climatic events on the Tibetan Plateau in shaping its genetic structure. We sequenced mitochondrial cytochrome b (cyt b) sequences in 103 individuals from 47 sampling sites. In addition, 23 cyt b sequences were collected from GenBank for analyses. Phylogenetic, demographic and landscape genetic methods were conducted. Seventy-six cyt b haplotypes were found and the genetic diversity was extremely high (π = 0.0368; h = 0.989). Five major evolutionary clades, based on geographic locations, were identified. Demographic analyses implied subclade 1A and subclade 1B experienced population expansions at about 0.052-0.013 Mya and 0.014-0.004 Mya, respectively. The divergence time analysis showed that the split between clade 1 and clade 2 occurred 0.26 Mya, which fell into the extensive glacial period (EGP, 0.5-0.17 Mya). The divergence times of other main clades (2.20-0.55 Mya) were congruent with the periods of the Qingzang Movement (3.6-1.7 Mya) and the Kun-Huang Movement (1.2-0.6 Mya), which were known as the most intense uplift events in the Tibetan Plateau. Our study supported the hypothesis that the SEMTP was a large late Pleistocene refugium, and further inferred that the Gongga Mountain Region and Hongya County were glacial refugia for A. draco in clade 1. We hypothesize that the evolutionary history of A. draco in the SEMTP primarily occurred in two stages. First, an initial divergence would have been shaped by uplift events of the Tibetan Plateau. Then, major glaciations in the Pleistocene added complexity to its demographic history and genetic structure

Risk scorecard to minimize impact of COVID-19 when reopening.

BACKGROUND: We present a novel approach for exiting coronavirus disease 2019 (COVID-19) lockdowns using a 'risk scorecard' to prioritize activities to resume whilst allowing safe reopening. METHODS: We modelled cases generated in the community/week, incorporating parameters for social distancing, contact tracing and imported cases. We set thresholds for cases and analysed the effect of varying parameters. An online tool to facilitate country-specific use including the modification of parameters (https://sshsphdemos.shinyapps.io/covid_riskbudget/) enables visualization of effects of parameter changes and trade-offs. Local outbreak investigation data from Singapore illustrate this. RESULTS: Setting a threshold of 0.9 mean number of secondary cases arising from a case to keep R 1. CONCLUSIONS: Countries can utilize a 'risk scorecard' to balance relaxations for travel and domestic activity depending on factors that reduce disease impact, including hospital/ICU capacity, contact tracing, quarantine and vaccination. The tool enabled visualization of the combinations of imported cases and activity levels on the case numbers and the trade-offs required. For vaccination, a reduction factor should be applied both for likelihood of an infected case being present and a close contact getting infected

Composite structural motifs of binding sites for delineating biological functions of proteins

Most biological processes are described as a series of interactions between proteins and other molecules, and interactions are in turn described in terms of atomic structures. To annotate protein functions as sets of interaction states at atomic resolution, and thereby to better understand the relation between protein interactions and biological functions, we conducted exhaustive all-against-all atomic structure comparisons of all known binding sites for ligands including small molecules, proteins and nucleic acids, and identified recurring elementary motifs. By integrating the elementary motifs associated with each subunit, we defined composite motifs which represent context-dependent combinations of elementary motifs. It is demonstrated that function similarity can be better inferred from composite motif similarity compared to the similarity of protein sequences or of individual binding sites. By integrating the composite motifs associated with each protein function, we define meta-composite motifs each of which is regarded as a time-independent diagrammatic representation of a biological process. It is shown that meta-composite motifs provide richer annotations of biological processes than sequence clusters. The present results serve as a basis for bridging atomic structures to higher-order biological phenomena by classification and integration of binding site structures.Comment: 34 pages, 7 figure

The sudden change phenomenon of quantum discord

Even if the parameters determining a system's state are varied smoothly, the behavior of quantum correlations alike to quantum discord, and of its classical counterparts, can be very peculiar, with the appearance of non-analyticities in its rate of change. Here we review this sudden change phenomenon (SCP) discussing some important points related to it: Its uncovering, interpretations, and experimental verifications, its use in the context of the emergence of the pointer basis in a quantum measurement process, its appearance and universality under Markovian and non-Markovian dynamics, its theoretical and experimental investigation in some other physical scenarios, and the related phenomenon of double sudden change of trace distance discord. Several open questions are identified, and we envisage that in answering them we will gain significant further insight about the relation between the SCP and the symmetry-geometric aspects of the quantum state space.Comment: Lectures on General Quantum Correlations and their Applications, F. F. Fanchini, D. O. Soares Pinto, and G. Adesso (Eds.), Springer (2017), pp 309-33