Electron delocalization triggers nonradical Fenton-like catalysis over spinel oxides.

Nonradical Fenton-like catalysis offers opportunities to overcome the low efficiency and secondary pollution limitations of existing advanced oxidation decontamination technologies, but realizing this on transition metal spinel oxide catalysts remains challenging due to insufficient understanding of their catalytic mechanisms. Here, we explore the origins of catalytic selectivity of Fe-Mn spinel oxide and identify electron delocalization of the surface metal active site as the key driver of its nonradical catalysis. Through fine-tuning the crystal geometry to trigger Fe-Mn superexchange interaction at the spinel octahedra, ZnFeMnO4 with high-degree electron delocalization of the Mn-O unit was created to enable near 100% nonradical activation of peroxymonosulfate (PMS) at unprecedented utilization efficiency. The resulting surface-bound PMS* complex can efficiently oxidize electron-rich pollutants with extraordinary degradation activity, selectivity, and good environmental robustness to favor water decontamination applications. Our work provides a molecule-level understanding of the catalytic selectivity and bimetallic interactions of Fe-Mn spinel oxides, which may guide the design of low-cost spinel oxides for more selective and efficient decontamination applications.

Tuning [VO6] Octahedron of Ammonium Vanadates via F Incorporation for High-Performance Aqueous Zinc Ion Batteries.

The electrochemical properties of vanadium-based materials as cathode materials for aqueous zinc ion batteries are still restricted by low conductivity, sluggish reaction kinetics, and poor structural stability. Herein, the [VO6] octahedron, as the basic unit of vanadium-oxide layer of ammonium vanadates (NH4V4O10, denoted as NVO), is incorporated by F atoms to regulate the coordinated environment of vanadium. Density functional theory (DFT) calculations and experimental results show that both physicochemical and electrochemical properties of NVO are improved by F-doping. The enhanced electronic conductivity accelerates the electron transfer and the expanded interlayer spacing expedites the diffusion kinetics of zinc ions. As a result, the F-doped NVO (F-NVO) electrode shows a high discharge capacity (465 mAh g-1 at 0.1 A g-1), good rate capability (260 mAh g-1 at 5 A g-1), and long-term cycling stability (88% capacity retention over 2000 cycles at 4 A g-1). The reaction kinetics and energy storage mechanism of F-NVO are further validated by in situ and ex situ characterizations.

In situ Raman investigation to electrochemical synthesis of ammonia on Pd nanocrystals.

Nitrate and nitrite are widely present in industrial wastewater and domestic sewage, so electrocatalytic reduction of both nitrate and nitrite to ammonia synthesis is considered to be a sustainable development approach. Pd nanostructures have attracted much attention because of their high activity in catalyzing the nitrate electrochemical reduction reaction. Here we prepare Pd nanocube and octahedron for the electrochemical reduction of nitrate and nitrite. It is found that Pd octahedron shows slightly higher activity toward nitrate reduction than Pd nanocube, while for nitrite reduction, Pd octahedron shows much higher activity than Pd nanocube. The ammonia yield rate is more potential-dependent. In situ Raman characterization further confirms the existence of adsorbed ammonia on the surface of nanocube and octahedron, indicating similar reduction pathways on (111)-facet octahedron and (100)-facet nanocube.

Improving Oxygen Reduction Performance of Surface-Layer-Controlled Pt-Ni Nano-Octahedra via Gaseous Etching.

This study demonstrates an atomic composition manipulation on Pt-Ni nano-octahedra to enhance their electrocatalytic performance. By selectively extracting Ni atoms from the {111} facets of the Pt-Ni nano-octahedra using gaseous carbon monoxide at an elevated temperature, a Pt-rich shell is formed, resulting in an ∼2 atomic layer Pt-skin. The surface-engineered octahedral nanocatalyst exhibits a significant enhancement in both mass activity (∼1.8-fold) and specific activity (∼2.2-fold) toward the oxygen reduction reaction compared with its unmodified counterpart. After 20,000 potential cycles of durability tests, the surface-etched Pt-Ni nano-octahedral sample shows a mass activity of 1.50 A/mgPt, exceeding the initial mass activity of the unetched counterpart (1.40 A/mgPt) and outperforming the benchmark Pt/C (0.18 A/mgPt) by a factor of 8. DFT calculations predict this improvement with the Pt surface layers and support these experimental observations. This surface-engineering protocol provides a promising strategy for developing novel electrocatalysts with improved catalytic features.

Unraveling the Synergistic Effect of Heteroatomic Substitution and Vacancy Engineering in CoFe2O4 for Superior Electrocatalysis Performance.

Metal ion substitution and anion exchange are two effective strategies for regulating the electronic and geometric structure of spinel. However, the optimal location of foreign metallic cations and the exact role of these metals and anions remain elusive. Herein, CoFe2O4-based hollow nanospheres with outstanding oxygen evolution reaction activity are prepared by Cr3+ substitution and S2- exchange. X-ray absorption spectra and theoretical calculations reveal that Cr3+ can be precisely doped into octahedral (Oh) Fe sites and simultaneously induce Co vacancy, which can activate adjacent tetrahedral (Td) Fe3+. Furthermore, S2- exchange results in structure distortion of Td-Fe due to compressive strain effect. The change in the local geometry of Td-Fe causes the *OOH intermediate to deviate from the y-axis plane, thus enhancing the adsorption of the *OOH. The Co vacancy and S2- exchange can adjust the geometric and electronic structure of Td-Fe, thus activating the inert Td-Fe and improving the electrochemical performance.

The Effects of Mono- and Bivalent Linear Alkyl Interlayer Spacers on the Photobehavior of Mn(II)-Based Perovskites.

Mn(II)-based perovskite materials are being intensively explored for lighting applications; understanding the role of ligands regarding their photobehavior is fundamental for their development. Herein, we report on two Mn (II) bromide perovskites using monovalent (perovskite 1, P1) and bivalent (perovskite 2, P2) alkyl interlayer spacers. The perovskites were characterized with powder X-ray diffraction (PXRD), electron spin paramagnetic resonance (EPR), steady-state, and time-resolved emission spectroscopy. The EPR experiments suggest octahedral coordination in P1 and tetrahedral coordination for P2, while the PXRD results demonstrate the presence of a hydrated phase in P2 when exposed to ambient conditions. P1 exhibits an orange-red emission, while P2 shows a green photoluminescence, as a result of the different types of coordination of Mn(II) ions. Furthermore, the P2 photoluminescence quantum yield (26%) is significantly higher than that of P1 (3.6 %), which we explain in terms of different electron-phonon couplings and Mn-Mn interactions. The encapsulation of both perovskites into a PMMA film largely increases their stability against moisture, being more than 1000 h for P2. Upon increasing the temperature, the emission intensity of both perovskites decreases without a significant shift in the emission spectrum, which is explained in terms of an increase in the electron-phonon interactions. The photoluminescence decays fit two components in the microsecond regime-the shortest lifetime for hydrated phases and the longest one for non-hydrated phases. Our findings provide insights into the effects of linear mono- and bivalent organic interlayer spacer cations on the photophysics of these kinds of Mn (II)-based perovskites. The results will help in better designs of Mn(II)-perovskites, to increase their lighting performance.

Ppb-Level Hydrogen Sulfide Gas Sensor Based on the Nanocomposite of MoS2 Octahedron/ZnO-Zn2SnO4 Nanoparticles.

Hydrogen sulfide (H2S) detection is extremely necessary due to its hazardous nature. Thus, the design of novel sensors to detect H2S gas at low temperatures is highly desirable. In this study, a series of nanocomposites based on MoS2 octahedrons and ZnO-Zn2SnO4 nanoparticles were synthesized through the hydrothermal method. Various characterizations such as X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectrum (XPS) have been used to verify the crystal phase, morphology and composition of synthesized nanocomposites. Three gas sensors based on the nanocomposites of pure ZnO-Zn2SnO4 (MS-ZNO-0), 5 wt% MoS2-ZnO-Zn2SnO4 (MS-ZNO-5) and 10 wt% MoS2-ZnO-Zn2SnO4 (MS-ZNO-10) were fabricated to check the gas sensing properties of various volatile organic compounds (VOCs). It showed that the gas sensor of (MS-ZNO-5) displayed the highest response of 4 to 2 ppm H2S and fewer responses to all other tested gases at 30 °C. The sensor of MS-ZNO-5 also displayed humble selectivity (1.6), good stability (35 days), promising reproducibility (5 cycles), rapid response/recovery times (10 s/6 s), a limit of detection (LOD) of 0.05 ppm H2S (Ra/Rg = 1.8) and an almost linear relationship between H2S concentration and response. Several elements such as the structure of MoS2, higher BET-specific surface area, n-n junction and improvement in oxygen species corresponded to improving response.

The Marriage of Sierpinski Triangles and Platonic Polyhedra.

Fractal structures with self-similarity are of fundamental importance in the fields of aesthetic, chemistry and mathematics. Here, by taking advantage of constructs the rational geometry-directed precursor design, we report the construction of two fascinating Platonic solids, the Sierpinski tetrahedron ST-T and the Sierpinski octahedron ST-O, in which each possesses a fractal Sierpinski triangle on their independent faces. These two discrete complexes are formed in near-quantitative yield from the multi-component self-assembly of truncated Sierpinski triangular kernel L1 with tribenzotriquinacene-based hexatopic and anthracene-based tetratopic terpyridine ligands (L3 and L4 ) in the presence of metal ions, respectively. The enhanced stabilities of the 3D discrete structures were investigated by gradient tandem mass spectrometry (gMS2 ). This work provides new constructs for the imitation of complex virus assemblies and for the molecular encapsulation of giant guest molecules.

A New Perspective and Design Principle for Halide Perovskites: Ionic Octahedron Network (ION).

The metal halide ionic octahedron, [MX6] (M = metal cation, X = halide anion), is considered to be the fundamental building block and functional unit of metal halide perovskites. By representing the metal halide ionic octahedron in halide perovskites as a super ion/atom, the halide perovskite can be described as an extended ionic octahedron network (ION) charge balanced by selected cations. This new perspective of halide perovskites based on ION enables the prediction of different packing and connectivity of the metal halide octahedra based on different solid-state lattices. In this work, a new halide perovskite Cs8Au3.5In1.5Cl23 was discovered on the basis of a BaTiO3-lattice ION {[InCl6][AuCl5][Au/InCl4]3}8-, which is assembled from three different ionic octahedra [InCl6], [AuCl6], and [Au/InCl6] and balanced by positively charged Cs cations. The success of this ION design concept in the discovery of Cs8Au3.5In1.5Cl23 opens up a new venue for the rational design of new halide perovskite materials.

Ligand-Free Processable Perovskite Semiconductor Ink.

Traditional covalent semiconductors require complex processing methods for device fabrication due to their high cohesive energies. Here, we develop a stable, ligand-free perovskite semiconductor ink that can be used to make patterned semiconductor-based optoelectronics in one step. The perovskite ink is formed via the dissolution of crystals of vacancy-ordered double perovskite Cs2TeX6 (X = Cl-, Br-, I-) in polar aprotic solvents, leading to the stabilization of isolated [TeX6]2- octahedral anions and free Cs+ cations without the presence of ligands. The stabilization of the fundamental perovskite ionic octahedral building blocks in solution creates multifunctional inks with the ability to reversibly transform between the liquid ink and the solid-state perovskite crystalline system in air within minutes. These easily processable inks can be patterned onto various materials via dropcasting, spraying or painting, and stamping, highlighting the crucial role of solvated octahedral complexes toward the rapid formation of phase-pure perovskite structures in ambient conditions.

On Topological Properties for Benzenoid Planar Octahedron Networks.

Chemical descriptors are numeric numbers that capture the whole graph structure and comprise a basic chemical structure. As a topological descriptor, it correlates with certain physical aspects in addition to its chemical representation of underlying chemical substances. In the modelling and design of any chemical network, the graph is important. A number of chemical indices have been developed in theoretical chemistry, including the Wiener index, the Randic index, and many others. In this paper, we look at the benzenoid networks and calculate the exact topological indices based on the degrees of the end vertices.

The catalytic and ROS-scavenging activities of green synthesized, antiferromagneticα-Fe2O3nanoparticle with a prismatic octahedron morphology from pomegranate rind extract.

Phenolic compounds (like 4-nitrophenol) and dyes (like methyl orange) are common by-products discharged by many industries as wastes; they are toxic and may induce discomfort and irritation in humans when ingested. Most of these compounds can be made less toxic through catalytic degradation. Metal oxide nanoparticles are found to have high catalytic activity and can degrade toxic phenolic compounds and dyes. In the current study, pomegranate rind extract was used for the green synthesis of iron oxide nanoparticles that exhibited an octahedron morphology revealed by scanning electron microscopy analysis. Energy dispersive x-ray analysis showed 47.96% content of Fe (by weight); high resolution-transmission electron microscopy analysis confirmed that the nanoparticles had a particle size of 22.54 ± 4.13 nm. The particles were further characterized by x-ray diffraction, fourier transform-infrared spectroscopy, vibrating sample magnetometer, and thermogravimetric analysis. The nanoparticle proved to be efficient in reducing 4-nitrophenol and methyl orange. It was also found to be non-toxic towards murine macrophages, RAW 264.7 with good ROS-scavenging potential compared to control.

Mn-O Covalency Governs the Intrinsic Activity of Co-Mn Spinel Oxides for Boosted Peroxymonosulfate Activation.

Transition metal (TM)-based bimetallic spinel oxides can efficiently activate peroxymonosulfate (PMS) presumably attributed to enhanced electron transfer between TMs, but the existing model cannot fully explain the efficient TM redox cycling. Here, we discover a critical role of TM-O covalency in governing the intrinsic catalytic activity of Co3-x Mnx O4 spinel oxides. Experimental and theoretical analysis reveals that the Co sites significantly raises the Mn valence and enlarges Mn-O covalency in octahedral configuration, thereby lowering the charge transfer energy to favor MnOh -PMS interaction. With appropriate MnIV /MnIII ratio to balance PMS adsorption and MnIV reduction, the Co1.1 Mn1.9 O4 exhibits remarkable catalytic activities for PMS activation and pollutant degradation, outperforming all the reported TM spinel oxides. The improved understandings on the origins of spinel oxides activity for PMS activation may inspire the development of more active and robust metal oxide catalysts.

Li2 BaSc(BO3 )2 F and LiBa2 Pb(BO3 )2 F with Layered Structures featuring Special Li-O/F Configurations.

Two new borate fluorides, Li2 BaSc(BO3 )2 F and LiBa2 Pb(BO3 )2 F, with layered structures featuring special Li-O/F configurations have been successfully prepared by the high-temperature solution method. Li2 BaSc(BO3 )2 F contains the first reported 2 ∞ [Li2 (BO3 )2 F] double layers that are evolved from 2 ∞ [Be2 BO3 F2 ] single layers in KBe2 BO3 F2 through substituting BeO4 with the LiO3 F tetrahedra. The adjacent double layers are tightly connected by strong Sc-O bonds, generating the strongest interlayer bond and smallest interlayer distance among KBe2 BO3 F2 derivatives with double-layered structures. LiBa2 Pb(BO3 )2 F features 2 ∞ [Li(BO3 )2 F] single layers built up of special LiO4 F2 octahedra and the BO3 triangles. To our best knowledge, the LiO4 F2 octahedron is observed for the first time in borates. Besides, the LiO4 F2 octahedra construct unique 1 ∞ [LiO4 F] straight chains through sharing apical F atoms, which is different from the configurations of the similar six-coordinated LiO6 octahedra in other borates.

Formation of Two-Dimensional Homologous Faults and Oxygen Electrocatalytic Activities in a Perovskite Nickelate.

Atomic-scale direct probing of active sites and subsequent elucidation of the structure-activity relationship are important issues involving oxide-based electrocatalysts to achieve better electrochemical conversion efficiency. By generating Ruddlesden-Popper (RP) two-dimensional homologous faults via simple control of the cation nonstoichiometry in LaNiO3 thin films, we demonstrate that strong tetragonal distortion of [NiO6] octahedra is induced by more than 20% elongation of Ni-O bonds in the faults. In addition to direct visualization of the elongation by scanning transmission electron microscopy, we identify that the distorted [NiO6] octahedra in the faults show considerably higher electrocatalytic activities than other surface sites during the electrochemical oxygen evolution reaction. This unequivocal evidence of the octahedral distortion and its impact on electrocatalysis in LaNiO3 suggests that the formation of RP-type faults can provide an efficient way to control the octahedral geometry and thereby remarkably enhance the oxygen catalytic performance of perovskite oxides.

Beyond Magic Numbers: Atomic Scale Equilibrium Nanoparticle Shapes for Any Size.

In the pursuit of complete control over morphology in nanoparticle synthesis, knowledge of the thermodynamic equilibrium shapes is a key ingredient. While approaches exist to determine the equilibrium shape in the large size limit (≳10-20 nm) as well as for very small particles (≲2 nm), the experimentally increasingly important intermediate size regime has largely remained elusive. Here, we present an algorithm, based on atomistic simulations in a constrained thermodynamic ensemble, that efficiently predicts equilibrium shapes for any number of atoms in the range from a few tens to many thousands of atoms. We apply the algorithm to Cu, Ag, Au, and Pd particles with diameters between approximately 1 and 7 nm and reveal an energy landscape that is more intricate than previously suggested. The thus obtained particle type distributions demonstrate that the transition from icosahedral particles to decahedral and further into truncated octahedral particles occurs only very gradually, which has implications for the interpretation of experimental data. The approach presented here is extensible to alloys and can in principle also be adapted to represent different chemical environments.

Competing Interactions between Various Entropic Forces toward Assembly of Pt3Ni Octahedra into a Body-Centered Cubic Superlattice.

Anisotropic nanocrystal assembled supercrystals with open superlattices (SLs) manifest novel and unique properties, but poor understanding of the nucleation/growth mechanisms limits their design and fabrication for practical applications. Using highly anisotropic Pt3Ni octahedral nanocrystals, we have grown large single supercrystals with an open body-centered cubic (bcc) superlattice that has a low filling factor of 26.8%. Synchrotron-based X-ray structural reconstruction fully revealed the coherence of translational and orientational orderings and determined that the constituent octahedra arrange themselves with the vertex-to-vertex and face-to-face configurations along the SL[100] and SL[111] directions, respectively. The large face-to-face separation and flexible vertex-to-vertex elastic contact provided the rattle space and supporting axis for local rotations of Pt3Ni octahedra within the bcc superlattice. Development of orientational disordering along with robust preservation of translational ordering during the heating process of a supercrystal in the oleic acid wetting environment confirmed the dominance of rotational entropy of hard octahedra in the formation of the open bcc superlattice. Ultimate achievement of dynamic equilibrium between the vertex-oriented elastic repulsions and the face-oriented attractions of surface-coating ligands governs the structural and mechanical stability of the supercrystal. This discovery provides significant insights into the design and control of geometrical shapes for the fabrication of highly anisotropic nanocrystals into desired open superlattices with tailored optical and electronic properties.

"114"-Type Nitrides LnAl(Si4-x Alx )N7 Oδ with Unusual [AlN6 ] Octahedral Coordination.

Aluminum-nitrogen six-fold octahedral coordination, [AlN6 ], is unusual and has only been seen in the high-pressure rocksalt-type aluminum nitride or some complex compounds. Herein we report novel nitrides LnAl(Si4-x Alx )N7 Oδ (Ln=La, Sm), the first inorganic compounds with [AlN6 ] coordination prepared via non-high-pressure synthesis. Structure refinements of neutron powder diffraction and single-crystal X-ray diffraction data show that these compounds crystallize in the hexagonal Swedenborgite structure type with P63 mc symmetry where Ln and Al atoms locate in anticuboctahedral and octahedral interstitials, respectively, between the triangular and Kagomé layers of [SiN4 ] tetrahedra. Solid-state NMR data of high-purity La-114 powders confirm the unusual [AlN6 ] coordination. These compounds are the first examples of the "33-114" sub-type in the "114" family. The additional site for over-stoichiometric oxygen in the structure of 114-type compounds was also identified.

A Capped Octahedral MHC6 Compound of a Platinum Group Metal.

A MHC6 complex of a platinum group metal with a capped octahedral arrangement of donor atoms around the metal center has been characterized. This osmium compound OsH{κ(2) -C,C-(PhBIm-C6 H4 )}3 , which reacts with HBF4 to afford the 14 e(-) species [Os{κ(2) -C,C-(PhBIm-C6 H4 )}(Ph2 BIm)2 ]BF4 stabilized by two agostic interactions, has been obtained by reaction of OsH6 (PiPr3 )2 with N,N'-diphenylbenzimidazolium chloride ([Ph2 BImH]Cl) in the presence of NEt3 . Its formation takes place through the C,C,C-pincer compound OsH2 {κ(3) -C,C,C-(C6 H4 -BIm-C6 H4 )}(PiPr3 )2 , the dihydrogen derivative OsCl{κ(2) -C,C-(PhBIm-C6 H4 )}(η(2) -H2 )(PiPr3 )2 , and the five-coordinate osmium(II) species OsCl{κ(2) -C,C-(PhBIm-C6 H4 )}(PiPr3 )2 .

Enhanced Pseudocapacitance in Multicomponent Transition-Metal Oxides by Local Distortion of Oxygen Octahedra.

Anomalously high pseudocapacitance of a metal oxide was observed when Ni, Co, and Mn were mixed in a solid solution. Analysis by X-ray absorption near-edge spectroscopy (XANES) identified a wider redox swing of Ni as the origin of the enlarged pseudocapacitance. Ab initio DFT calculations revealed that aliovalent species resulting from the copresence of multiple transition metals can generate permanent local distortions of [NiO6] octahedra. As this type of distortion breaks the degenerate eg level of Ni(2+), the Jahn-Teller lattice instability necessary for the Ni(2+/3+) redox flip can be effectively diminished during charge-discharge, thus resulting in the significantly increased capacitance. Our findings highlight the importance of understanding structure-property correlation related to local structural distortions in improving the performance of pseudocapacitors.