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Creators/Authors contains: "Ni, Danrui"

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  1. Pyroxenes (AMX2O6) consisting of infinite one-dimensional edge-sharing MO6chains and bridging XO4tetrahedra are fertile ground for finding quantum materials. Thus, here, we have studied calcium cobalt germanate (CaCoGe2O6) and calcium cobalt silicate (CaCoSi2O6) crystals in depth. Heat capacity data show that the spins in both compounds are dominantly Ising-like, even after being manipulated by high magnetic fields. On cooling below the Néel temperatures, a sharp field–induced transition in magnetization is observed for CaCoGe2O6, while multiple magnetization plateaus beneath the full saturation moment are spotted for CaCoSi2O6. Our analysis shows that these contrasting behaviors potentially arise from the different electron configurations of germanium and silicon, in which the 3d orbitals are filled in the former but empty in the latter, enabling electron hopping. Thus, silicate tetrahedra can aid the interchain superexchange pathway between cobalt(II) ion centers, while germanate ones tend to block it during magnetization. 
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  2. Electronic structure calculations indicate that the Sr2FeSbO6double perovskite has a flat-band set just above the Fermi level that includes contributions from ordinary subbands with weak kinetic electron hopping plus a flat subband that can be attributed to the lattice geometry and orbital interference. To place the Fermi energy in that flat band, electron-doped samples with formulas Sr2-xLaxFeSbO6(0 ≤x≤ 0.3) were synthesized, and their magnetism and ambient temperature crystal structures were determined by high-resolution synchrotron X-ray powder diffraction. All materials appear to display an antiferromagnetic-like maximum in the magnetic susceptibility, but the dominant spin coupling evolves from antiferromagnetic to ferromagnetic on electron doping. Which of the three subbands or combinations is responsible for the behavior has not been determined. 
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  3. The previously unreported layered compounds IrTe 2 I and RhTe 2 I were prepared by a high-pressure synthesis method. Single crystal X-ray and powder X-ray diffraction studies find that the compounds are isostructural, crystallizing in a layered orthorhombic structure in the non-centrosymmetric, non-symmorphic space group Pca 2 1 (#29). Characterization reveals diamagnetic, high resistivity, semiconducting behavior for both compounds, consistent with the +3 chemical valence and d 6 electronic configurations for both iridium and rhodium and the Te–Te dimers seen in the structural study. Electronic band structures are calculated for both compounds, showing good agreement with the experimental results. 
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  4. [Mn(bpy)(CO) 3 Br] is recognized as a benchmark electrocatalyst for CO 2 reduction to CO, with the doubly reduced [Mn(bpy)(CO) 3 ] − proposed to be the active species in the catalytic mechanism. The reaction of this intermediate with CO 2 and two protons is expected to produce the tetracarbonyl cation, [Mn(bpy)(CO) 4 ] + , thereby closing the catalytic cycle. However, this species has not been experimentally observed. In this study, [Mn(bpy)(CO) 4 ][SbF 6 ] ( 1 ) was directly synthesized and found to be an efficient electrocatalyst for the reduction of CO 2 to CO in the presence of H 2 O. Complex 1 was characterized using X-ray crystallography as well as IR and UV-Vis spectroscopy. The redox activity of 1 was determined using cyclic voltammetry and compared with that of benchmark manganese complexes, e.g. , [Mn(bpy)(CO) 3 Br] ( 2 ) and [Mn(bpy)(CO) 3 (MeCN)][PF 6 ] ( 3 ). Infrared spectroscopic analyses indicated that CO dissociation occurs after a single-electron reduction of complex 1 , producing a [Mn(bpy)(CO) 3 (MeCN)] + species. Complex 1 was experimentally verified as both a precatalyst and an on-cycle intermediate in homogeneous Mn-based electrocatalytic CO 2 reduction. 
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