Microporosity and Catalytic Activity for Hydrodesulfurization of Pharmacosiderite Mo4P3O16 Synthesized at a Moderate Temperature.

Pharmacosiderite Mo4P3O16 (Pharma-MoPO) consists of [Mo4O4] cubane unit and [PO4] tetrahedral to form an open framework with a microporous structure similar to that of LTA-type zeolite. Although attractive applications are expected due to its microporous structure and redox-active components, its physicochemical properties have been poorly investigated due to the specificity of its synthesis, which requires a high hydrothermal synthesis temperature of 360 °C. In this study, we succeeded in synthesizing Pharma-MoPO by hydrothermal synthesis at 230 °C, which can be applied using a commercially available autoclave by changing the metal source. Through the study of the solids and liquids obtained after hydrothermal syntheses, the formation process of Pharma-MoPO under our studied synthesis conditions was proposed. Advanced characterizations provided detailed structural information on Pharma-MoPO, including the location site of a countercation NH4+. Pharma-MoPO could adsorb CO2 with the amount close to the number of cages without removing NH4+. Pharma-MoPO exhibited stable catalytic activity for the hydrodesulfurization of thiophene while maintaining its crystal structure, except for the introduction of sulfide by replacing lattice oxygens. Pharmacosiderite Mo4P3O16 was successfully obtained by hydrothermal synthesis at a moderate temperature, and its microporosity for CO2 adsorption and catalytic properties for hydrodesulfurization were discovered.

A Zeolitic Octahedral Metal Oxide with Ultrahigh Porosity for High-temperature and High-humidity Alkyne/Alkene Separation.

Zeolitic octahedral metal oxide is a newly synthesized all-inorganic zeolitic material and has been used for adsorption, separation, and catalysis. Herein, a new zeolitic octahedral metal oxide was synthesized and characterized. The porous framework was established through the assembly of [P2Mo13O50] clusters with PO4 linkers. Guest molecules occupied the framework, which could be removed through heat treatment, thereby opening the micropores. The pore characteristics were controlled by the cations within the micropore, enabling the adjustment of the interactions with alkynes and alkenes. This resulted in good separation performance of ethylene/acetylene and propylene/propyne even under high temperature and humidity conditions. The high stability of the material enabled the efficient recovery and reuse without discernible loss in the separation performance. Due to the relatively weak interaction between the adsorbed alkyne and the framework, the adsorbent facilitated the recovery of a highly pure alkyne. This feature enhances the practical applicability of the material in various industrial processes.

Metal-Support Interaction in Gold Zeolitic Octahedral Metal Oxide and the Catalytic Activity for Low-Temperature Alcohol Oxidation.

Au nanoparticles are efficient catalysts for selective oxidations. The interaction between Au nanoparticles and supports is critical for achieving high catalytic activity. Herein, Au nanoparticles are supported on a zeolitic octahedral metal oxide based on Mo and V. The charge of Au is controlled by the surface oxygen vacancies of the supports, and the redox property of the zeolitic vanadomolybdate is highly dependent on Au loading. The Au-supported zeolitic vanadomolybdate is used as a heterogeneous catalyst for alcohol oxidation under mild conditions with molecular oxygen as an oxidant. The supported Au catalyst can be recovered and reused without the loss of activity.

Molybdenum Oxide Constructed by {Mo6O21}6- Pentagonal Unit Assembly and Its Redox Properties.

Molybdenum oxides are widely used in various fields due to their electronic and structural characteristics. These materials can generate lattice oxygen defects by reduction treatments, which sometimes play central roles in various applications. However, little has been understood about their properties since it is difficult to increase the amount of lattice oxygen defects due to the crystal structure changes in most cases. Here, we report a new class of high-dimensionally structured Mo oxide (HDS-MoOx) constructed by the random assembly of {Mo6O21}6- pentagonal units (PUs). Since the PU is a stable structural unit, the structural network based on the PU hardly caused structural changes to make the lattice oxygen defects vanish. Consequently, HDS-MoOx could generate a substantial amount of lattice oxygen defects, and their amount was controllable, at least in the range of MoO2.64-MoO3.00. HDS-MoOx was more redox active than typical Mo oxide (α-MoO3) and demonstrated an oxidation ability for gas-phase isopropanol oxidation under the reaction conditions, whereas α-MoO3 affords no oxidation products.

Oxidation Catalysis over Solid-State Keggin-Type Phosphomolybdic Acid with Oxygen Defects.

Keggin-type phosphomolybdic acid (PMo12O40), treated with pyridine (Py), forms a crystalline material (PyPMo-HT) following heat treatment under an inert gas flow at ∼420 °C. Although this material is known to have attractive catalytic properties for gas-phase oxidation, the origin of this catalytic activity requires clarification. In this study, we investigated the crystal structure of PyPMo-HT. PyPMo-HT comprises a one-dimensional array of Keggin units and pyridinium cations (HPy), with an HPy/Keggin unit ratio of ∼1.0. Two oxygen atoms were removed from the Keggin unit during crystal structure transformation, which resulted in an electron being localized on the Mo atom in close contact with the adjacent Keggin unit. Upon the introduction of molecular oxygen, electron transfer from this Mo atom resulted in the formation of an electrophilic oxygen species that bridged two Keggin units. The electrophilic oxygen species acted as a catalytically active oxygen species, as confirmed by the selective oxidation of propylene. PyPMo-HT showed excellent catalytic activity for the selective oxidation of methacrolein, with the methacrylic acid yield being superior to that obtained with PMo12O40 and comparable to that obtained with an industrial Keggin-type polyoxometalate (POM) catalyst. The oxidation catalysis observed over PyPMo-HT provides a deeper understanding of POM-based industrial catalytic processes.

Assembly of ϵ-Keggin Polyoxometalate from Molecular Crystal to Zeolitic Octahedral Metal Oxide.

Zeolitic octahedral metal oxides are inorganic crystalline microporous materials with adsorption and redox properties. New ϵ-Keggin nickel molybdate-based zeolitic octahedral metal oxides have been synthesized. 31 P NMR spectroscopy shows that reduction of MoVI -based molybdates forms an ϵ-Keggin polyoxometalate that immediately transfers to the solid phase. Investigation of the formation process indicates that a low Ni concentration, insoluble reducing agent, and long synthesis time are the critical factors for obtaining the zeolite octahedral metal oxides rather than the ϵ-Keggin polyoxometalate molecule. The synthesized zeolitic nickel molybdate with Na+ is used as the adsorbent, which effectively separates C2 hydrocarbon mixtures.

Investigation of the Synthesis of Zeolitic Vanadotungstate and its Use in the Separation of Propylene/Propane at High Temperature and Humidity.

Synthetic conditions for the zeolitic octahedral metal oxide based on vanadotungstate are studied. The temperature, time, acidity, W/V ratio, cation species, and concentration affect the resulting materials. The study shows that mixing tungstate and VO2+ in an aqueous solution generates cubane units ([W4O16]8-) at room temperature. The cubane units assemble with VO2+ immediately to form a solid with an amorphous phase and nonporosity, which further crystallizes under a hydrothermal condition to form the crystalline microporous vanadotungstate. The zeolitic vanadotungstates act as effective adsorbents for the separation of propylene/propane. The active materials effectively separate propylene/propane even at high temperatures and high humidities.

A Zeolitic Octahedral Metal Oxide with Ultra-Microporosity for Inverse CO2 /C2 H2 Separation at High Temperature and Humidity.

Separation of CO2 /C2 H2 to obtain pure C2 H2 presents a challenge for the chemical industry. CO2 -selective adsorbents are favored because of the convenient separation process. However, there are only a few CO2 -selective adsorbents that can effectively isolate CO2 from CO2 /C2 H2 , and there is almost no research on CO2 /C2 H2 separation under harsh conditions, such as with high temperatures and humidities. Herein, a zeolitic octahedral metal oxide based on ϵ-Keggin polyoxometalates is utilized for separations of CO2 /C2 H2 at high temperatures and humidities. Single gas adsorption measurements show that the material only adsorbs CO2 with almost no C2 H2 taken up. Dynamic competitive adsorption experiments show that the material efficiently separates CO2 /C2 H2 , and highly pure C2 H2 is obtained directly. The robust material maintains a high separation performance at 333 K with 18.12 % water. The high stability of the material enables reuse without loss of separation performance.

Zeolitic Vanadotungstates with Ultrahigh Porosities for Separation of Butane and Isobutane.

Zeolitic vanadotungstates with tunable microporosity have potential interests in gas separation. The pore openings of the materials are in between the diameters of normal butane and isobutane, which causes the materials only adsorb normal butane. The breakthrough experiments show that the materials effectively separate normal butane from the normal butane and isobutane mixture even at high temperatures. The robust materials can be reused without loss of the separation performance.

Synthesis of Zeolitic Mo-Doped Vanadotungstates and Their Catalytic Activity for Low-Temperature NH3-SCR.

Mo was successfully introduced into a vanadotungstate (VT-1), which is a crystalline microporous zeolitic transition-metal oxide based on cubane clusters [W4O16]8- and VO2+ linkers (MoxW4-x. x: number of Mo in VT-1 unit cell determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES)). It was confirmed that W in the cubane units was substituted by Mo. The resulting materials showed higher microporosity compared with VT-1. The surface area and the micropore volume increased to 296 m2·g-1 and 0.097 cm3·g-1, respectively, for Mo0.6W3.4 compared with the those values for VT-1 (249 m2·g-1 and 0.078 cm3·g-1, respectively). The introduction of Mo changed the acid properties including the acid amount (VT-1: 1.06 mmol g-1, Mo0.6W3.4: 2.18 mmol·g-1) and its strength because of the changes of the chemical bonding in the framework structure. MoxW4-x showed substantial catalytic activity for the selective catalytic reduction of NO with NH3 (NH3-selective catalytic reduction (SCR)) at a temperature as low as 150 °C.

Zeolitic Octahedral Metal Oxides with Ultra-Small Micropores for C2 Hydrocarbon Separation.

Separation of C2 hydrocarbons, C2 H6 , C2 H4 , and C2 H2 , remains significant challenges in chemical industry. However, there are only few adsorbents that can effectively isolate C2 hydrocarbons from their mixtures particularly at a high temperature. Herein, we design a zeolitic octahedral metal oxide based on ϵ-Keggin polyoxometalates with metal ion linkers. Single gas adsorption of the material shows the different adsorption performances for the C2 hydrocarbons and the strong interaction of the material with the C2 hydrocarbons. Dynamic competitive adsorption experiments show that the material efficiently separates each of the binary C2 hydrocarbon mixtures and even the ternary C2 hydrocarbon mixtures with high selectivity. The material keeps high separation performance even the temperature was increased to 85 °C. The material is stable and is able to be reused without loss of the separation performance.

Vanadium-Enhanced Intramolecular Redox Property of a Transition-Metal Oxide Molecular Wire.

Transition-metal oxide molecular wires are inorganic 1D polymers with elemental diversity. The properties of the materials are tuned by tuning the chemical compositions. The phosphovanadomolybdate molecular wire is synthesized, which is an isostructural material of the phosphomolybdate molecular wire. V is randomly located in the crystal to form {[(HPIIIO3)(MoVI5O15)(VVO3)]3-}n, which is incorporated into the material after the formation of the phosphomolybdate molecular wire. The heat-triggered redox reaction via the intramolecular electron-transfer and oxygen-transfer procedure is promoted after V substitution. Oxygen transfers from {VVO6} to {HPIIIO3}, and an electron transfers from {HPIIIO3} to {VVO6} with oxidation of the triangle {HPIIIO3} to the corner-sharing tetrahedral {PV2O7} and reduction of the octahedral {VVO6} to the pyramidal {VIVO5}. The material shows catalytic activity for the aerobic oxidation of alcohol to aldehyde, and good activity with high selectivity is obtained.

Synthesis of High Dimensionally Structured Mo-Fe Mixed Metal Oxide and Its Catalytic Activity for Selective Oxidation of Methanol.

High-dimensionally structured Mo-Fe oxide (HDS-MoFeO) was synthesized through an assembly of structural units supplied from Keplerate-type polyoxometalate, {Mo72Fe30}, under an appropriate hydrothermal condition. HDS-MoFeO showed excellent catalytic activity for the selective oxidation of methanol with slightly lower selectivity for formaldehyde than that of a conventional Mo-Fe oxide catalyst.

Synthesis of Fluoride-Containing High Dimensionally Structured Nb Oxide and Its Catalytic Performance for Acid Reactions.

High dimensionally structured niobium oxide (HDS-NbO) containing fluoride (F-) was prepared by a hydrothermal synthesis. F- could be introduced into HDS-NbO by replacing lattice oxygen up to a solid F-/Nb ratio of 0.55. The introduction of an appropriate amount of F- promoted the crystal growth of HDS-NbO, while niobium oxyfluoride having the hexagonal tungsten bronze structure (HTB-Nb(F,O)x) was concomitantly formed by excess F- addition. HAADF-STEM analysis suggested that the number of micropores (hexagonal and heptagonal channels) in HDS-NbO was increased by the introduction of an appropriate amount of F-. The catalytic activity for Brønsted acid reactions was evaluated by Friedel-Crafts alkylation. The catalytic activity was significantly increased by the introduction of F-, while excess introduction of F- significantly decreased the activity. Catalytic activity for the Lewis acid reaction in the presence of water was evaluated by the transformation of pyruvaldehyde into lactic acid. The catalytic activity was changed by the introduction of F- in a manner similar to that observed in the Friedel-Crafts alkylation. On the basis of the results obtained, we propose that the local catalyst structure around the micropores of HDS-NbO is crucial for the acid reactions.

Intramolecular Electron Transfer and Oxygen Transfer of Phosphomolybdate Molecular Wires.

Phosphomolybdates with different P species exhibiting a 1D molecular structure are synthesized. The materials are constructed by a {[MoVI6O21]6-}n molecular tube as a shell with trapping a redox-active species P in the center. The building units ([(HPIIIO3)MoVI6O18]2- or [(PV2O7)MoVI12O36]4-) form at room temperature, which further polymerize linearly along the c-axis. Interestingly, the material shows an unusual heat-triggered intramolecular redox property, which undergoes an electron-transfer-oxygen-transfer procedure from [{(HPIIIO3)MoVI6O18]2-}n to {[(PV2O7)MoVI12O36]4-}n/2. The crystal structure of the material is stable during the oxidation reaction, while the central P is oxidized and the local structure changes.

Redox-Active Zeolitic Transition Metal Oxides Based on ε-Keggin Units for Selective Oxidation.

The design and development of zeolitic transition metal oxides for selective oxidation are interesting due to the combination of the redox properties and microporosities. Redox-active zeolitic transition metal oxides based on ε-Keggin iron molybdates were synthesized. O2 can be activated by the materials via an electron-transfer-based process, and the materials can be oxidized even at room temperature. The materials are oxidized and reduced reversibly while the crystal structures are maintained. V is uniformly incorporated in the materials without changing the basic structures, and the redox properties of the materials are tuned by V. The materials are used as robust catalysts for ethyl lactate oxidation to form ethyl pyruvate using O2 as an oxidant.

[Solitary lymph node metastasis from early-stage hepatocellular carcinoma after transcatheter arterial chemoembolization and radiofrequency ablation: a case report and review of the Japanese literature].

A 77-year-old man with chronic hepatitis C underwent transcatheter arterial chemoembolization (TACE) and radiofrequency ablation (RFA) for early-stage hepatocellular carcinoma (HCC) in segment 8 of the liver. Necrosis was confirmed radiologically. After 19 months, recurrent HCC in segment 6 was treated with TACE and RFA. There was no recurrence. Direct-acting antiviral (DAA) therapy 24 months after the initial procedure led to a sustained virologic response. AFP-L3 markedly increased 11 months after DAA therapy, and MRI 6 months after that showed a solitary lymph node near the common bile duct. Because no intrahepatic recurrence or other lymph nodes were seen, the solitary node was excised. Histopathology showed metastatic HCC. There has been no subsequent recurrence over 13 months of follow-up.

Ultrathin Anionic Tungstophosphite Molecular Wire with Tunable Hydrophilicity and Catalytic Activity for Selective Epoxidation in Organic Media.

The extended 1D tungstophosphite molecular wire is obtained by connection of polyoxometalates. Self-assembly of a triangular PIII O3 unit with tungstate produces a hexagonal [HPIII W6 O21 ]2- building block, which then connects linearly to form the molecular wire. The surface property of the molecular wire is tuned to hydrophobic using organoammonium cations, and the surface-modified material disperses easily in organic media. The multifunctional material, which possesses nanostructure, hydrophobicity, and redox properties simultaneously, is suitable for olefin epoxidation in organic solvent.

The Assembly of an All-Inorganic Porous Soft Framework from Metal Oxide Molecular Nanowires.

An all-inorganic soft framework is rare but interesting for both fundamental research and practical applications. Here, an all-inorganic soft framework based on a transition metal oxide is reported. The periodic connection of a one-dimensional anionic tungstoselenate molecular wire building block with a CoII ion is used to construct the crystalline material. The crystal structure of the material was determined by high-angle annular dark-field scanning transmission electron microscopy combined with several characterization techniques. The soft framework of the material enables water adsorption/desorption with a change in its structure, leading to a high level of water adsorption. The framework of the material is flexible, and the structure of the molecular wire building block is stable during the water adsorption/desorption process.

Structural Characterization of 2D Zirconomolybdate by Atomic Scale HAADF-STEM and XANES and Its Highly Stable Electrochemical Properties as a Li Battery Cathode.

The structural determination of nanomaterials and their application in energy storage and transfer are of great importance. Herein, a layered zirconomolybdate with a two-dimensional structure was synthesized. Atomic resolution electron microscopy was utilized for direct visualization of the structure that was further confirmed by powder X-ray diffraction and X-ray absorption near-edge structure analyses. The structure of the molecular sheet was stable at a high temperature in an oxidative atmosphere. The electrochemical performance of the material was evaluated with a Li battery composed of the calcined material as a cathode. Li ions were reversibly inserted and extracted between the layers without collapse of the structure of the material. The electrochemical properties of the material were derived from the reversible redox activity of the Mo ions and Zr ions in the material as well as the flexibility of the molecular layer of the material.