Hongil Jo

Pb2BO3Cl: A Tailor‐Made Polar Lead Borate Chloride with Very Strong Second Harmonic Generation

A meticulously designed, polar, non-centrosymmetric lead borate chloride, Pb2 BO3 Cl, was synthesized using KBe2 BO3 F2 (KBBF) as a model. Single-crystal X-ray diffraction revealed that the structure of Pb2 BO3 Cl consists of cationic [Pb2 (BO3 )](+) honeycomb layers and Cl(-) anions. Powder second harmonic generation (SHG) measurements on graded polycrystalline Pb2 BO3 Cl indicated that the title compound is phase-matchable (type I) and exhibits a remarkably strong SHG response, which is approximately nine times stronger than that of potassium dihydrogen phosphate, and the largest efficiency observed in materials with structures similar to KBBF. Further characterization suggested that the compound melts congruently at high temperature and has a wide transparency window from the near-UV to the mid-IR region.

ACdCO3F (A = K and Rb): new noncentrosymmetric materials with remarkably strong second-harmonic generation (SHG) responses enhanced via π-interaction

Two new noncentrosymmetric (NCS) materials, namely, ACdCO3F (A = K and Rb) containing both a d10 cation (Cd2+) and a π-conjugated parallel carbonate anion (CO32−), were synthesized through conventional solid state reactions. ACdCO3F exhibits a 3-dimensional structure that is composed of the stacked layers of [Cd(CO3)]∞. Each [Cd(CO3)]∞ layer is connected by infinite Cd–F–Cd chains and the [CO3] triangles are oriented in the same direction with a coplanar alignment. KCdCO3F and RbCdCO3F reveal remarkably strong second-harmonic generation (SHG) responses of approximately 9.0 and 7.2 times that of potassium dihydrogen phosphate (KDP), respectively, and both materials are phase-matchable. ACdCO3F exhibit wide transparent regions ranging from far UV to mid IR. Theoretical calculations confirm that the large SHG efficiencies indeed originate from enhancement via interatomic interactions between the s and p states of Cd2+ and the π-conjugated groups of the [CO3]2− unit within the [Cd(CO3)]∞ layers.

Influence of Ca-doping in layered perovskite PrBaCo2O5+δ on the phase transition and cathodic performance of a solid oxide fuel cell

Layered perovskite oxides with the formula LnBaCo2O5+δ (Ln = Pr, Nd, Sm and Gd) have received attention as promising cathode materials for solid oxide fuel cells (SOFCs) because of their high oxygen diffusion and surface exchange coefficients. Recently, many researchers have reported that substituting barium with strontium or calcium can increase the structural stability, electrical conductivity, and catalytic activity of LnBaCo2O5+δ. In this study, we investigated the effect of Ca doping on the structural, electrical, and electrochemical properties of PrBa1−xCaxCo2O5+δ (x = 0, 0.1, 0.2, 0.3 and 0.4). Increasing the amount of Ca dopant changed the structure of PrBa1−xCaxCo2O5+δ from a layered perovskite to a simple perovskite. At x = 0.3, co-existence of the simple and the layered perovskite structure is observed. Electrical conductivity and electro-chemical performance were improved with increasing amount of Ca in the layered perovskite structure and declined with increasing amount of the simple perovskite phase.

Hexagonal tungsten oxide nanoflowers as enzymatic mimetics and electrocatalysts

Tungsten oxide (WOx) has been widely studied for versatile applications based on its photocatalytic, intrinsic catalytic, and electrocatalytic properties. Among the several nanostructures, we focused on the flower-like structures to increase the catalytic efficiency on the interface with both increased substrate interaction capacities due to their large surface area and efficient electron transportation. Therefore, improved WOx nanoflowers (WONFs) with large surface areas were developed through a simple hydrothermal method using sodium tungstate and hydrogen chloride solution at low temperature, without any additional surfactant, capping agent, or reducing agent. Structural determination and electrochemical analyses revealed that the WONFs have hexagonal Na0.17WO3.085·0.17H2O structure and exhibit peroxidase-like activity, turning from colorless to blue by catalyzing the oxidation of a peroxidase substrate, such as 3,3′,5,5′-tetramethylbenzidine, in the presence of H2O2. Additionally, a WONF-modified glassy carbon electrode was adopted to monitor the electrocatalytic reduction of H2O2. To verify the catalytic efficiency enhancement by the unique shape and structure of the WONFs, they were compared with calcinated WONFs, cesium WOx nanoparticles, and other peroxidase-like nanomaterials. The results indicated that the WONFs showed a low Michaelis-Menten constant (km), high maximal reaction velocity (vmax), and large surface area.

Polar Noncentrosymmetric ZnMoSb2O7 and Nonpolar Centrosymmetric CdMoSb4O10: d10 Transition Metal Size Effect Influencing the Stoichiometry and the Centricity

Two new quaternary molybdenum(VI) antimony(III) oxides, ZnMoSb2O7 and CdMoSb4O10, have been synthesized in phase-pure form. The title compounds consist of highly polarizable cations, i.e., d(0) (Mo(6+)) and d(10) (Zn(2+) or Cd(2+)), and lone-pair cations (Sb(3+)). ZnMoSb2O7 exhibits a three-dimensional framework with ZnO4, MoO4, and SbO4 polyhedra in the polar space group P21, whereas CdMoSb4O10 exhibits one-dimensional tubule structures with CdO6, MoO4, and SbO3 polyhedra in the space group P21/m. Several synthetic efforts suggest that the the dissimilar radii of Zn(2+) and Cd(2+) that can accommodate polyhedra of Sb(3+) cations influence the stoichiometry as well as the centricity for the reported materials. Spectroscopic, thermal, and elemental analyses are reported along with dipole moment calculations. Nonlinear optical properties and their structural origin are examined for polar ZnMoSb2O7 as well.

Rb3VO(O2)2CO3: A Four‐in‐One Carbonatoperoxovanadate Exhibiting an Extremely Strong Second‐Harmonic Generation Response

A nonlinear optical (NLO) carbonatoperoxovanadate, Rb3 VO(O2 )2 CO3 , was synthesized through a simple solution-evaporation method in phase-pure form. Single-crystal X-ray diffraction revealed that the structure of Rb3 VO(O2 )2 CO3 consists of important noncentrosymmetric (NCS) chromophores, that is, π-delocalized (CO3 )2- groups, a second-order Jahn-Teller (SOJT) distortive V5+ cation, and π-localized distorted O22- groups, as well as charge-balancing polarizable Rb+ ions. The powder second-harmonic generation (SHG) measurements indicated that Rb3 VO(O2 )2 CO3 is phase-matchable (Type I) and exhibits a remarkably strong SHG response circa 21.0 times that of potassium dihydrogen phosphate (KDP), which is the largest efficiency observed among carbonate NLO materials. First-principles calculation analysis suggests that the extremely large SHG response of Rb3 VO(O2 )2 CO3 is attributed to the synergistic effect of the cooperation of all the constituting NCS chromophores.

Photoconversion Mechanisms and the Origin of Second-Harmonic Generation in Metal Iodates with Wide Transparency, NaLn(IO3)4 (Ln = La, Ce, Sm, and Eu) and NaLa(IO3)4:Ln3+ (Ln = Sm and Eu)

Four new metal iodates, namely, NaLn(IO3)4 (Ln = La, Ce, Sm, and Eu), and a series of NaLa(IO3)4:Ln3+ (Ln = Sm and Eu) solid solutions were synthesized through hydrothermal reactions. The structures of the title compounds are similar to that of NaY(IO3)4 crystallizing in the acentric monoclinic space group Cc. The iodate materials reveal layered structures composed of LnO8 square antiprisms and IO3 polyhedra, in which each layer is connected by the I···O interactions. NaLa(IO3)4 suggests a great potential as a matrix for optical source attributed to its acentricity and broad transparency from visible to mid-IR region. The photoluminescence properties depending on the concentration of Sm3+ reveal that NaLa(IO3)4:Sm3+ undergoes a self-quenching relaxation over 7 mol % of Sm3+ by dipole-quadrupole interactions. Attributable to the asymmetric coordination environment of Ln3+, stronger electric dipole transitions compared to magnetic dipole transitions were observed for both compounds. In addition, the materials exhibit strong second-harmonic generation (SHG) responses and are type I phase-matchable. The structural origin of the SHG properties for the reported iodates is elucidated.

Cationic Site-Preference in the Yb14-xCaxAlSb11 (4.81 ≤ x ≤ 10.57) Series: Theoretical and Experimental Studies

Four quaternary Zintl phases with mixed-cations in the Yb14-xCaxAlSb11 (4.81 ≤ x ≤ 10.57) series have been synthesized by using the arc-melting and the Sn metal-flux reaction methods, and the isotypic crystal structures of the title compounds have been characterized by both powder and single-crystal X-ray diffraction (PXRD and SXRD) analyses. The overall crystal structure adopting the Ca14AlSb11-type can be described as a pack of four different types of the spiral-shaped one-dimensional octahedra chains with various turning radii, each of which is formed by the distorted ((Yb/Ca)Sb6) octahedra. Four symmetrically-independent cationic sites contain mixed occupations of Yb2+ and Ca2+ with different mixing ratios and display a particular site preference by two cationic elements. Two hypothetical structural models of Yb4Ca10AlSb11 with different cationic arrangements were designed and exploited to study the details of site and bond energies. QVAL values provided the rationale for the observed site preference based on the electronegativity of each atom. Density of states (DOS) curves indicated a semiconducting property of the title compounds, and crystal orbital Hamilton population (COHP) plots explained individual chemical bonding between components. Thermal conductivity measurement was performed for Yb8.42(4)Ca5.58AlSb11, and the result was compared to compounds without mixed cations.

Effect of MultiSubstitution on the Thermoelectric Performance of the Ca11−xYbxSb10−yGez (0 ≤ x ≤ 9; 0 ≤ y ≤ 3; 0 ≤ z ≤ 3) System: Experimental and Theoretical Studies

The Zintl phase solid-solution Ca11-xYbxSb10-yGez (0 ≤ x ≤ 9; 0 ≤ y ≤ 3; 0 ≤ z ≤ 3) system with the cationic/anionic multisubstitution has been synthesized by molten Sn metal flux and arc-melting methods. The crystal structure of the nine title compounds were characterized by both powder and single-crystal X-ray diffractions and adopted the Ho11Ge10-type structure with the tetragonal space group I4/mmm (Z = 4, Pearson Code tI84). The overall isotypic structure of the nine title compounds can be illustrated as an assembly of three different types of cationic polyhedra sharing faces with their neighboring polyhedra and the three-dimensional cage-shaped anionic frameworks consisting of the dumbbell-shaped Sb2 units and the square-shaped Sb4 or (Sb/Ge)4 units. During the multisubstitution trials, interestingly, we observed a metal-to-semiconductor transition as the Ca and Ge contents increased in the title system from Yb11Sb10 to Ca9Yb2Sb7Ge3 (nominal compositions) on the basis of a series of thermoelectric property measurements. This phenomenon can be elucidated by the suppression of a bipolar conduction of holes and electrons via an extra hole-carrier doping. The tight-binding linear muffin-tin orbital calculations using four hypothetical structural models nicely proved that the size of a pseudogap and the magnitude of the density of states at the Fermi level are significantly influenced by substituting elements as well as their atomic sites in a unit cell. The observed particular cationic/anionic site preferences, the historically known abnormalities of atomic displacement parameters, and the occupation deficiencies of particular atomic sites are further rationalized by the QVAL value criterion on the basis of the theoretical calculations. The results of SEM, EDS, and TGA analyses are also provided.

Syntheses, Structures, and Characterization of Quaternary Tellurites, Li3MTe4O11 (M = Al, Ga, and Fe)

Three new quaternary lithium metal tellurites, Li3MTe4O11 (M = Al, Ga, and Fe), have been synthesized through hydrothermal and solid-state reactions by heating a mixture of LiOH·H2O, TeO2, and M2O3. The structures of the title compounds have been determined by single-crystal and powder X-ray diffraction. Li3MTe4O11 reveal three-dimensional (3D) frameworks that consist of MO6 octahedra, TeO3 trigonal pyramids, and TeO4 polyhedra. The variable coordination mode of Te4+ within the framework leads to the formation of 1D channels that host Li+ cations on both tetrahedral and octahedral sites. The bulk and grain boundary Li+ ion conductivities for a Li3FeTe4O11 pellet in open air are estimated to be 1.0 × 10-4 and 2.7 × 10-6 S cm-1, respectively, at room temperature from the impedance profile analysis. A lower activation energy of 19.9 kJ mol-1 is obtained for the system, which is similar to that of Li10GeP2S12 (24 kJ mol-1). Detailed characterizations such as thermal, spectroscopic, and magnetic properties for the reported materials are also reported.