We present in situ high-pressure synchrotron X-ray diffraction (XRD) and Raman spectroscopy study, and electrical transport measurement of single crystal WSe2 in diamond anvil cells with pressures up to 54.0-62.8 GPa. The XRD and Raman results show that the phase undergoes a pressure-induced iso-structural transition via layer sliding, beginning at 28.5 GPa and not being completed up to around 60 GPa. The Raman data also reveals a dominant role of the in-plane strain over the out-of plane compression in helping achieve the transition. Consistently, the electrical transport experiments down to 1.8 K reveals a pressure-induced metallization for WSe2 through a broad pressure range of 28.2-61.7 GPa, where a mixed semiconducting and metallic feature is observed due to the coexisting low-and high-pressure structures.

Phase-selective synthesis and structure switching behavior of a functional material are essential to enable comparative studies on the structure-property relationship. Here, we report a controllable fluorination route to phase-pure erbium oxyfluorides with orthorhombic (O-ErOF) and rhombohedral (R-ErOF) structures. This facile method adopts polytetrafluoroethylene (PTFE) as the fluoridizer, and the phase selectivity can be easily achieved at specific fluorination temperatures. The phase evolution and detailed crystal structures of erbium oxyfluoride were characterized by powder X-ray diffraction (PXRD) at various sintering temperatures and Rietveld refinements, respectively. An irreversible phase transition from O-ErOF to R-ErOF was observed under heating around 600 degrees C. The upconversion (UC) luminescence properties of R-ErOF and O-ErOF were studied comparatively by means of photoluminescence, P-I, and UC decay curves. Despite their similar components and crystal structure, R-ErOF exhibits stronger (more than 20 times) red UC emission than O-ErOF. The anomalous UC behavior of the two polymorphs of ErOF was associated with the energy transfer processes dependent on their crystal structure.

Nitrogen doping via high-temperature ammonization is a frequently used strategy to extend the light harvesting capacity of wide-bandgap catalysts in the visible region. Under such a reductive atmosphere, the reduction of transition metals is supposed to occur, however, this has not been thoroughly studied yet. Here, by combining chemically-controlled doping and subsequent liquid exfoliation, ultra-thin [Nb3O8](-) nanosheets with separate N doping, reduced-Nb doping and N/reduced-Nb codoping were fabricated for comparative studies on the doping effect for photocatalytic hydrogen evolution. Layered KNb3O8 was used as the starting material and the above-mentioned three doping conditions were achieved by high-temperature treatment with urea, hydrogen and ammonia, respectively. The morphology, crystal and electronic structures, and the catalytic activity of the products were characterized thoroughly by means of TEM, AFM, XRD, XPS, EPR, absorption spectroscopy and photocatalytic hydrogen evolution. Significantly, the black N/reduced-Nb co-doped monolayer [Nb3O8](-) nanosheets exhibit the mostly enhanced photocatalytic hydrogen generation rate, indicating a synergistic doping effect of the multiple chemical-design strategy. The modified electronic structure of [Nb3O8](-) nanosheets and the role of exotic dopants in bandgap narrowing are put forward for the rational design of better photocatalysts with reduced-metal self-doping.

Hydrogen production by catalytic water splitting using sunlight holds great promise for clean and sustainable energy source. Despite the efforts made in the past decades, challenges still exist in pursuing solid catalysts with light-harvesting capacity, large surface areas and efficient utilities of the photogenerated carrier, at the same time. Here, a multiple structure design strategy leading to highly enhanced photocatalytic performance on hydrogen production from water splitting in Dion-Jacobson perovskites KCa2Nan-3NbnO3n+1 is described. Specifically, chemical doping (N/Nb4+) of the parent oxides via ammoniation improved the ability of sunlight harvesting efficiently; subsequent liquid exfoliation of the doped perovskites yielded ultrathin [Ca2Nan-3NbnO3n+1](-) nanosheets with greatly increased surface areas. Significantly, the maximum hydrogen evolution appears in the n=4 nanosheets, which suggests the most favorable thickness for charge separation in such perovskite-type catalysts. The optimized black N/Nb4+-[Ca2NaNb4O13](-) nanosheets show greatly enhanced photocatalytic performance, as high as 973 mu molh(-1) with Pt loading, on hydrogen evolution from water splitting. As a proof-of-concept, this work highlights the feasibility of combining various chemical strategies towards better catalysts and precise thickness control of two-dimensional materials.

Weyl semimetal defines a material with three-dimensional Dirac cones, which appear in pair due to the breaking of spatial inversion or time reversal symmetry. Superconductivity is the state of quantum condensation of paired electrons. Turning a Weyl semimetal into superconducting state is very important in having some unprecedented discoveries. In this work, by doing resistive measurements on a recently recognized Weyl semimetal TaP under pressures up to about 100 GPa, we show the concurrence of superconductivity and a structure transition at about 70 GPa. It is found that the superconductivity becomes more pronounced when decreasing pressure and retains when the pressure is completely released. High-pressure x-ray diffraction measurements also confirm the structure phase transition from I4(1)md to P-6m2 at about 70 GPa. More importantly, ab-initial calculations reveal that the P-6m2 phase is a new Weyl semimetal phase and has only one set of Weyl points at the same energy level. Our discovery of superconductivity in TaP by high pressure will stimulate investigations on superconductivity and Majorana fermions in Weyl semimetals.

We report on the discovery of a pressure-induced topological and superconducting phase of SnSe, a material which attracts much attention recently due to its superior thermoelectric properties. In situ high-pressure electrical transport and synchrotron x-ray diffraction measurements show that the superconductivity emerges along with the formation of a CsCl-type structural phase of SnSe above around 27 GPa, with amaximum critical temperature of 3.2 K at 39 GPa. Based on ab initio calculations, this CsCl-type SnSe is predicted to be a Dirac line-node (DLN) semimetal in the absence of spin-orbit coupling, whose DLN states are protected by the coexistence of time-reversal and inversion symmetries. These results make CsCl-type SnSe an interesting model platform with simple crystal symmetry to study the interplay of topological physics and superconductivity.

We present in situ high-pressure synchrotron x-ray diffraction (XRD) and electrical transport measurements on quasi-one-dimensional single-crystal TiS3 up to 29.9-39.0 GPa in diamond-anvil cells, coupled with first-principles calculations. Counterintuitively, the conductive behavior of semiconductor TiS3 becomes increasingly insulating with pressure until P-C1 similar to 12 GPa, where extremes in all three axial ratios are observed. Upon further compression to P-C2 similar to 22 GPa, the XRD data evidence a structural phase transition. Based on our theoretical calculations, this structural transition is determined to be isosymmetric, i.e., without change of the structural symmetry (P2(1)/m), mainly resulting from rearrangement of the dangling S-2 pair along the a axis.

Topological semimetal, a novel state of quantum matter hosting exotic emergent quantum phenomena dictated by the nontrivial band topology, has emerged as a new frontier in condensed-matter physics. Very recently, the coexistence of triply degenerate points of band crossing and Weyl points near the Fermi level was theoretically predicted and experimentally identified in MoP. Via high-pressure electrical transport measurements, we report here the emergence of pressure-induced superconductivity in MoP with a critical transition temperature T-c of ca. 2.5 K at ca. 30 GPa. No structural phase transition is observed up to ca. 60 GPa via synchrotron X-ray diffraction study. Accordingly, the topologically nontrivial band protected by the crystal structure symmetries and superconductivity are expected to coexist at pressures above 30 GPa, consistent with density functional theory calculations. Thus, the pressurized MoP represents a promising candidate of topological superconductor. Our finding is expected to stimulate further exploitation of exotic emergent quantum phenomena in novel unconventional fermion system.

Tetradymite-type topological insulator Sn-doped Bp 101S0.9Te2S (Sn-BSTS), with a surface state Dirac point energy well isolated from the bulk valence and conduction bands, is an ideal platform for studying the topological transport phenomena. Here, we present high-pressure transport studies on single-crystal Sn-BSTS, combined with Raman scattering and synchrotron x-ray diffraction measurements. Over the studied pressure range of 0.7-37.2 GPa, three critical pressure points can be observed: (i) At similar to 9 GPa, a pressure-induced topological insulator-to-metal transition is revealed due to closure of the bulk band gap, which is accompanied by changes in slope of the Raman frequencies and a minimum in da within the pristine rhombohedral structure (R-3m); (ii) at similar to 13 GPa, superconductivity is observed to emerge, along with the R-3m to a C2/c (monoclinic) structural transition; (iii) at similar to 24 GPa, the superconducting transition onset temperature T-c reaches a maximum of similar to 12K, accompanied by a second structural transition from the C2/c to a body-centered cubic Im -3m phase.

Estimation of daily downward shortwave radiation (DSR) is of great importance in global energy budget and climatic modeling. The combination of satellite-based instantaneous measurements and temporal extrapolation models is the most feasible way to capture daily radiation variations at large scales. However, previous studies did not pay enough attention to topographic effects and simple temporal extrapolation methods were applied directly to rugged terrains which cover a large amount of the land surface. This paper, divided into two parts, aims at analyzing the topographic uncertainties of existing models and proposing a better method based on a mountain radiative transfer (MRT) model to calculate daily DSR. As the first part, this paper analyze the spatiotemporal variations of DSR influenced by topographic effects and checks the applicability of three temporal extrapolation methods on cloud-free days. Considering that clouds also have a strong influence on solar radiation, cloud-free days are chosen for targeted analysis of topographic effects on DSR. Three indices, the coefficient of variation, entropy-based dispersion coefficient (CH), and sill of semivariogram, are put forward to give a quantitative description of spatial heterogeneity. Our results show that the topography can dramatically strengthen the spatial heterogeneity of DSR. The index, CH, has an advantage for quantifying spatial heterogeneity as it offers a tradeoff between accuracy and efficiency. Spatial heterogeneity distorts the daily variation of DSR. Application of extrapolation methods in rugged terrains leads to overestimation of daily average DSR up to 60 W/m2 and a maximum 200 W/m2 error of instantaneous DSR on cloud-free days. This paper makes a quantitative analysis of topographic effects under different spatiotemporal conditions, which lays the foundation for developing a new extrapolation method.