Single Transition-Metal Atom Anchored on a Rhenium Disulfide Monolayer: An Efficient Bifunctional Electrocatalyst for the Oxygen Evolution and Oxygen Reduction Reactions.

Developing efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) bifunctional electrocatalysts is attractive for rechargeable metal-air batteries. Meanwhile, single metal atoms embedded in 2D layered transition metal chalcogenides (TMDs) have become a very promising catalyst. Recently, many attentions have been paid to the 2D ReS2 electrocatalyst due to its unique distorted octahedral 1T' crystal structure and thickness-independent electronic properties. Here, the catalytic activity of different transition metal (TM) atoms embedded in ReS2 using the density functional theory is investigated. The results indicate that TM@ReS2 exhibits outstanding thermal stability, good electrical conductivity, and electron transfer for electrochemical reactions. And the Ir@ReS2 and Pd@ReS2 can be used as OER/ORR bifunctional electrocatalysts with a lower overpotential for OER (ηOER) of 0.44 V and overpotentials for ORR (ηORR) of 0.26 V and 0.27 V, respectively. The excellent catalytic activity is attributed to the optimal adsorption strength for oxygen intermediates coming from the effective modulation of the electronic structure of ReS2 after Ir/Pd doping. The results can help to deeply understand the catalytic activity of TM@ReS2 and develop novel and highly efficient OER/ORR electrocatalysts.

The enhanced bandgap and birefringence of rare-earth phosphates XPO4 (X = Sc, Y, La, and Lu): a first-principles investigation.

Rare-earth phosphates were thought to be good candidates as ultraviolet/deep ultraviolet optical materials due to their relatively large bandgap and optical properties. In this paper, the authors screened out a family of XPO4 (X = Sc, Y, La, and Lu) compounds with an enhanced bandgap (HSE06 bandgap ≥ 7.61 eV) and birefringence (0.0934-0.2003@1064 nm) using first-principles calculations. The origin of enhanced optical properties was investigated using projected density of states, distortion indices, and Born effective charges. The results show that the PO4 anionic groups and X-O polyhedra give the main contribution in determining the optical properties, and the PO4 anionic groups give more contribution than other functional basic units. The spin-orbit interaction was also investigated. Similar band structures were found after spin-orbit coupling (SOC) was considered, and slightly enhanced birefringence was found when SOC was applied to these rare-earth phosphates.

Deep-Ultraviolet Transparent Mixed Metal Sulfamates with Enhanced Nonlinear Optical Properties and Birefringence.

Enhancing anisotropy through the controlled arrangement of anionic groups is essential for improving the nonlinear optical (NLO) performance of non-π-conjugated NLO materials. In this study, we present the successful synthesis of the first examples of mixed alkali metal-alkaline earth metal sulfamate materials, including noncentrosymmetric Cs2 Mg(NH2 SO3 )4 ⋅ 4H2 O (1), as well as centrosymmetric K2 Ca(NH2 SO3 )4 (2) and Rb2 Ca(NH2 SO3 )4 (3). All three compounds feature promising deep ultraviolet cut-off edges, notably 1 with a cut-off edge below 180 nm. The synergy of Cs+ and Mg2+ cations in 1 facilitated the successful alignment of polar [NH2 SO3 ] tetrahedra in a uniform orientation. Remarkably, 1 stands as the sole instance among reported sulfamate compounds with a co-parallel anionic arrangement, yielding a very large dipole moment compared to other non-π-conjugated NLO materials. Moreover, the substantial dipole moment of 1 yields an enhanced second harmonic generation response, approximately 2.3 times that of KH2 PO4 , and a large birefringence of 0.054 at 546.1 nm. The approach of regulating the arrangement of anionic groups using aliovalent cations holds promise for advancing the exploration of non-π-conjugated NLO materials.

Controlling the Nonlinear Optical Behavior and Structural Transformation with A-Site Cation in α-AZnPO4 (A = Li, K).

Regulating the crystal structure by A-site cation substitution is one of the effective methods to explore high-performance nonlinear optical (NLO) materials. Herein, two non-centrosymmetric (NCS) compounds, α-MZnPO4 (M = Li, K) with short UV absorption edges 221 and 225 nm, are obtained by performing A-site cation substitution method. It is noteworthy that α-LiZnPO4 (α-LZPO) achieves >10 times second harmonic generation (SHG) response (2.3 × KDP) enhancement compared with that of α-KZnPO4 (α-KZPO) (0.2 × KDP), which is the only case among phosphates with different A-site cations. By structural comparison, it is found that the A-site cations play important roles for anion rearrangements, and further the structure features of the two compounds by designing two suppositional crystal models as well as performing other theoretical calculations are analyzed. The study confirms the feasibility to design promising NLO materials with strengthen SHG response and structural stability in orthophosphate system.

Four New Sb-based Orthophosphates: Cation Regulation to Investigate Diversified Structural Architecture.

In the work, four new Sb-based phosphates, K4 (SbO2 )5 (PO4 )3 , Rb(SbO2 )2 PO4 , Rb3 (SbO2 )3 (PO4 )2 and Cs3 (SbO2 )3 (PO4 )2 (H2 O)1.32 , were successfully synthesized by a high-temperature melt method. Among them, Rb(SbO2 )2 PO4 and Rb3 (SbO2 )3 (PO4 )2 are the first reported examples of Rb-containing alkali metal Sb-based phosphates. They show three-dimensional (3D) frameworks composed of [Sb8 P4 O30 ]∞ layer for K4 (SbO2 )5 (PO4 )3 and [Sb6 P2 O20 ]∞ layer for Rb(SbO2 )2 PO4 , and 2D lamellar structure composed of [Sb3 P2 O10 ]∞ for Rb3 (SbO2 )3 (PO4 )2 and Cs3 (SbO2 )3 (PO4 )2 (H2 O)1.32 . A detailed structural comparison shows that the structure dimensions for them transfer from 1D to complex 3D framework with the increase of (Sb+P)/O ratio, which affects performances of the compounds. Optical property and energy band structure calculations were also carried out based on the density functional theory (DFT). The present study enriches the diversity of Sb-based phosphates and paves the way for further explore their optical properties in the future.

Li3B8O13X (X = Cl and Br): Two New Noncentrosymmetric Crystals with Large Birefringence Induced by BO3 Units.

Enthusiasm for the exploration of nonlinear alkali metal borates remains high. Focusing on the Li-B-O-X (X = Cl and Br) system, two examples of noncentrosymmetric borates, Li3B8O13Cl and Li3B8O13Br, were obtained using a high-temperature solution method under vacuum conditions. Structurally, the Li3B8O13X crystals exhibit two independent alternately arranged three-dimensional B-O network structures formed by the basic building block unit B8O16. The performance measurements demonstrate their short ultraviolet cutoff edges. The theoretical calculation indicates that the BO3 units dominate the contribution to their large optical anisotropy with the birefringence, 0.094 and 0.088@1064 nm for Li3B8O13Cl and Li3B8O13Br, respectively.

Mechanisms of adsorption and diffusion of Na on a VSe2 monolayer with engineering-induced vacancies.

Although research on vacancy engineering of anode materials has sufficiently advanced to obtain heightened battery capacity, the effect on the diffusion barrier underlying the mechanism remains to be elucidated. Herein, we investigated the effect of vacancy engineering on Na adsorption and diffusion on a vanadium diselenide (VSe2) monolayer using first-principles calculations to reveal the underlying physics behind the performance optimization of anode materials in a sodium-ion battery. The results demonstrate that the structure of the substrate is responsible for the difference between the adsorption energy and diffusion barrier that resulted from cation and anion vacancies. As there is an absent Se atom (VSe) on the surface layer of the substrate, diffusion of Na on the surface could become pressurized with a high diffusion barrier up to 0.33 eV and a high adsorption energy (-1.92 eV) to capture additional Na atoms. However, because the V layer is sandwiched between two Se layers, there is less interaction with Na, and the adsorption energy and diffusion barrier are -1.58 and 0.13 eV, respectively, when a V atom is nonexistent (VV). Moreover, the defective VSe2 increased the battery capacity, with little impact on open-circuit voltage. In this work, we analyzed the effect of vacancy engineering on VSe2 monolayer material, which provides theoretical clues for the design of efficient sodium-ion batteries with heightened capacity.

Pb18 O8 Cl15 I5 : A Polar Lead Mixed Oxyhalide with Unprecedented Architecture and Excellent Infrared Nonlinear Optical Properties.

To develop high-performance nonlinear optical (NLO) materials for infrared (IR) applications, we have applied a rational element-composition design strategy and investigated the unexplored PbO-PbCl2 -PbI2 system. By doing so, we discovered a new polar lead mixed oxyhalide, Pb18 O8 Cl15 I5 , the first synthetic metal oxyhalide combining both Cl- and I- . Pb18 O8 Cl15 I5 reveals an unprecedented structural feature with two different dimensional types of oxocentered Pb-O units, namely, [O4 Pb8 ]8+ clusters and [OPb2 ]2+ chains. Centimeter-sized single crystals of Pb18 O8 Cl15 I5 have been successfully grown under ambient conditions. Remarkably, Pb18 O8 Cl15 I5 satisfies all fundamental yet rigorous criteria for high-performance IR NLO materials, exhibiting the widest IR transparency (up to 16.0 µm) among oxide-based crystals, strong second-harmonic generation response (1.05×AgGaS2 ), superior birefringence (0.086 at 636 nm), and a high laser-induced damage threshold (8.5×AgGaS2 ).

Two Pyrophosphates with Large Birefringences and Second-Harmonic Responses as Ultraviolet Nonlinear Optical Materials.

Two new pyrophosphates nonlinear optical (NLO) materials, Rb3 PbBi(P2 O7 )2 (I) and Cs3 PbBi(P2 O7 )2 (II), were successfully designed and synthesized. Both compounds exhibit large NLO effects and birefringences. Material I presents the scarce case of possessing the coexistence of large birefringence (0.031 at 1064 nm and 0.037 at 532 nm) and second harmonic generation (SHG) response (2.8× potassium dihydrogen phosphate (KDP)) in ultraviolet NLO phosphates and its SHG is the largest in the phase-matching (PM) pyrophosphates. Both I and II have three-dimensional (3D) crystal structures composed of corner-shared RbO12 (CsO11 ), RbO10 (CsO10 ), BiO6 , PbO7 (PbO6 ) and P2 O7 groups, in which P2 O7 and PbO7 (PbO6 ) units form an alveolate [PbPO]∞ skeleton frame. Theoretical calculations reveal that the P-O, Bi-O and Pb-O units are mainly responsible for the moderate birefringence and large SHG efficiency of I.

A Joint Strategy To Evaluate the Microscopic Origin of the Second-Harmonic-Generation Response in Nonpolar ABCO3F Compounds.

In this paper, a joint strategy was proposed to investigate the microscopic origin of the second-harmonic-generation (SHG) response in nonpolar ABCO3F compounds. The SHG coefficients of ABCO3F were evaluated using finite-field and sum-over-states methods. The tendency of the obtained SHG tensors is in good agreement with the powder SHG response. The atomic contribution was investigated using variation of the atomic charges and bandwidth of occupied atomic states. The results show that oxygen states play a key role in determining the SHG response, and the neighboring divalent cations exert a indirect influence via covalent interaction. The bidentate bonding pattern is beneficial to obtaining a largely enhanced SHG response.

ALiZnP2O7 (A = Rb, Cs): Two Mixed Alkali Zinc Pyrophosphates Featuring a [Li2Zn2P4O20]14- Anionic Skeleton.

Two new isotypic diphosphates, RbLiZnP2O7 (RLZP) and CsLiZnP2O7 (CLZP), have been synthesized by a high-temperature solid-phase method. They both crystallize in the Pnma space group (No. 62) and have similar crystal configurations. ALiZnP2O7 (A = Rb, Cs) consists of a [Li2Zn2P4O20]14- anionic skeleton, which is composed of Li/ZnO4 tetrahedral and diphosphate groups, and the Rb or Cs atoms are located in the large hole. In this paper, we discuss the structures of the title compounds and isonomic AA'ZnP2O7 (A = alkali metal); it is found that the ionic radii of the cations and bond angles have an effect on the symmetry of the compounds. By analysis, we found that the M/P values have some effect on the dimensionality of the anionic groups in phosphates containing P2O7 groups. Thermal and spectral analyses are carried out on the title compounds. Besides that mentioned above, we also studied the relationship between the electronic structures and optical properties by theoretical calculations.

Pb2Ba3(BO3)3Cl: A Material with Large SHG Enhancement Activated by Pb-Chelated BO3 Groups.

Pb(II) has long been associated with lone pair activity and is often substituted in alkali earth metal borates to create new nonlinear optical (NLO) materials with enhanced second harmonic generation (SHG) capabilities. However, large enhancement in isomorphic Pb-free analogues is rare. Here we report a new NLO material Pb2Ba3(BO3)3Cl with a phase-matching SHG response approximately 3.2× that of KDP and 6× higher than its isomorphic compound Ba5(BO3)3Cl. We show that the enhanced SHG response originates from a unique edge-sharing connection between lead-oxygen polyhedra and boron-oxygen groups, making the dielectric susceptibility more easily affected by the external electric field of an incident photon. This understanding provides a route to identify systems that would benefit from SHG-active cation substitution in isomorphic structures that exhibit weak or null SHG responses.

Contribution of lone-pairs to birefringence affected by the Pb(II) coordination environment: a DFT investigation.

Pb(II) cations have long been associated with lone-pairs which can help to enhance the optical anisotropic birefringence. In this paper, the contribution of lead cations to birefringence has been investigated using first-principles and real-space atom-cutting methods. The results show that the contribution of lead cations to birefringence is determined by the degree of stereochemical activity, which is affected by the coordination environment of lead cations.

Cs3Zn6B9O21: a chemically benign member of the KBBF family exhibiting the largest second harmonic generation response.

Nonlinear optical (NLO) crystals are essential materials for generation of coherent UV light in solid state lasers. KBBF is the only material that can achieve coherent light below 200 nm by direct second harmonic generation (SHG). However, its strong layer habits and the high toxicity of the beryllium oxide powders required for synthesis limit its application. By substituting Be with Zn and connecting adjacent [Zn2BO3O2]∞ layers by B3O6 groups, a new UV nonlinear optical material, Cs3Zn6B9O21, was synthesized. It overcomes the processing limitations of KBBF and exhibits the largest SHG response in the KBBF family.

The influence of hydrogen bonding on the nonlinear optical properties of a semiorganic material NH4B[D-(+)-C4H4O5]2·H2O: a theoretical perspective.

In this work, a potential semiorganic nonlinear optical candidate NH4B[D-(+)-(C4H4O5)]2·H2O (NBC) has been studied using Density Functional Theory. The origin of the second harmonic generation (SHG) effect of NBC crystals for the NH4B[D-(+)-(C4H4O5)]2·H2O molecular complex is explained by employing a combination of the density of states, SHG density and molecular orbital analysis. It reveals a way in which the organic and ammonium groups affect the SHG processes in a significantly different manner in the crystals and the molecular complex. In particular, the role of hydrogen bonding interaction in influencing the electronic structure and nonlinear optical properties is explicitly identified and explained.

Triterpenoid saponins from the rhizomes of Anemone flaccida and their inhibitory activities on LPS-induced NO production in macrophage RAW264.7 cells.

A new ursane-type triterpenoid saponin, flaccidoside IV (1), and three new oleanane-type triterpenoid saponins, flaccidosides V-VII (2-4), along with 17 known saponins (5-21), were isolated from the rhizomes of Anemone flaccida. The structures of the new triterpenoid saponins were determined based on spectroscopic analyses and chemical methods. All the isolated saponins were tested for their inhibitory activities on lipopolysaccharide-induced nitric oxide production in RAW264.7 macrophages, and several bisdesmosidic oleanane-type triterpenoid saponins (2, 7, and 10) showed significant inhibitory activities, which indicated they had potential anti-inflammatory activities under their noncytotoxic concentrations in vitro.

The Spin-Orbit Effect on the Electronic Structures, Refractive Indices, and Birefringence of X2PO4I (X = Pb, Sn, Ba and Sr): A First-Principles Investigation.

Introducing post-transition metal cations is an excellent strategy for enhancing optical properties. This paper focuses on four isomers, namely the X2PO4I (X = Pb, Sn, Ba, and Sr) series. For the first time, the paper's attention is paid to the changes in electronic structure, as well as refractive indices and birefringence, with and without the inclusion of spin-orbit effects in this series. The first-principles results show that spin-orbit effects of the 5p and 6p states found in these compounds lead to splitting of the bands, narrowing of the band gap, enhancement of the lone-pair stereochemistry, and enhancement of the refractive indices and birefringence. Moreover, a comparison of the lone-pair electron phosphates, X2PO4I (X = Pb and Sn), and the isomeric alkaline earth metal phosphates, X2PO4I (X = Ba and Sr), reveals that changes in the band structure have a greater effect on the enhancement of the birefringence than the slight enhancement of the lone-pair stereochemical activity. This study has important implications for a deeper understanding of the optical properties of crystals and the design of novel optical materials.

Structural characterisation and optical properties of new alkaline earth phosphate CaMg(P4O12) and alkaline alumophosphate Cs3Al4(PO4)5.

Two new family members of mixed alkali-earth metal phosphate and aluminophosphate CaMg(P4O12) and Cs3Al4(PO4)5 were prepared from a phosphate system using a high-temperature solution method. The structural analysis results show that two compounds crystallize in the monoclinic space group C2/c and P21/n and feature a three-dimensional (3D) network. The 3D structure of CaMg(P4O12) consists of [CaO6], [MgO6] octahedra and [P4O12] rings, in which the [MgO6] and [P4O12] rings link to form a 3D structure and Ca2+ cations are filled within the structure. Interestingly, for compound Cs3Al4(PO4)5, its structure features 4, 8, and 12-ring channels with [Al2O4O4P2O4], [Al4O8O8P4O8] and [Al6O12O12P6O12] units as BBUs, respectively; the Cs+ cations are located in the cavities. Furthermore, IR spectral analysis and thermal properties are discussed. UV-vis-NIR diffuse reflectance spectroscopy data show that the UV cutoff edges of CaMg(P4O12) are below 200 nm. Remarkably, in order to determine optical properties and the structure-properties relationship, theoretical calculations were adopted. Electronic structure calculations demonstrate that CaMg(P4O12) has an indirect band gap with the value of 5.86 eV, and Cs3Al4(PO4)5 has a direct band gap of 5.21 eV.

Novel antimony phosphates with enlarged birefringence induced by lone pair cations.

Phosphates, whose obvious disadvantage is the relatively small birefringence, can be overcome by the introduction of post-transition metal cations containing stereochemically active lone-pair electrons. In this paper, two new compounds were successfully explored in the A-Sb-P-O system, i.e. Cs2Sb3O(PO4)3 (CsSbPO) and (NH4)2Sb4O2(H2O)(PO4)2[PO3(OH)]2 (NH4SbPOH). Transmission spectra show that CsSbPO has a surprising transmission range with a UV cutoff edge of 213 nm. First-principles calculations show that both compounds have a wide band gap (5.02 eV for CsSbPO and 5.30 eV for NH4SbPOH) and enlarged birefringence (Δn = 0.034@1064 nm for CsSbPO and Δn = 0.045@1064 nm for NH4SbPOH). The results of real-space atom-cutting investigations show that the distorted [SbOx] polyhedra originating from the asymmetric lone pair electrons give the main contribution to the total birefringence and overcome the disadvantage of small birefringence of phosphates but maintain wide transition windows.

Study on the thermoluminescence and optically stimulated luminescence of LiMgPO4:Dy phosphors synthesized by different methods.

LiMgPO4:Dy phosphors were synthesized by high-temperature solid-state method and sol-gel method. The effects of different synthesis methods on crystal structure, morphology, thermoluminescence (TL) properties, and optically stimulated luminescence (OSL) properties of LiMgPO4:Dy were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), TL glow curve and continuous wave OSL (CW-OSL) curves. XRD patterns showed that the crystal phase of the samples synthesized by the two methods is LiMgPO4. The morphology of the samples synthesized by sol-gel method was better than that synthesized by high-temperature solid-state method. The TL sensitivity of the samples synthesized by sol-gel method was higher than that synthesized by high-temperature solid-state method. The TL strongest glow peak of the LiMgPO4:Dy sample synthesized by high-temperature solid-state method was 363 K, while that the LiMgPO4:Dy sample synthesized by sol-gel method was 380 K. The OSL sensitivity of the samples synthesized by sol-gel method was significantly higher than that synthesized by high-temperature solid-state method. The synthesis method had no effect on the OSL decay of the sample. LiMgPO4:Dy phosphor synthesized by sol-gel method may be a suitable candidate material for radiation dosimetry.