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.

Preparation and isolation of mono-Nb substituted Keggin-type phosphomolybdic acid and its application as an oxidation catalyst for isobutylaldehyde and Wacker-type oxidation.

The potassium and proton mixed salt of mono-Nb substituted Keggin-type phosphomolybdate, KH3[PMo11NbO40], was isolated in a pure form by reacting Keggin-type phosphomolybdic acid (H3[PMo12O40]) and potassium hexaniobate (K8Nb6O19) in water, followed by freeze-drying. The all protonic form, H4[PMo11NbO40], was isolated via proton exchange with H-resin and subsequent freeze-drying. The most crucial factor to isolate KH3[PMo11NbO40] and H4[PMo11NbO40] in pure forms is the evaporation of water using the freeze-drying method. Using a similar procedure, the potassium salt of the di-Nb substituted compound K5[PMo10Nb2O40] was isolated. H4[PMo11NbO40] exhibited high catalytic activity for oxidizing isobutylaldehyde to methacrolein and moderate catalytic activity for the Wacker-type oxidation of allyl phenyl ether when combined with Pd(OAc)2.

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.

Serrated polyps in patients with ulcerative colitis: Unique clinicopathological and biological characteristics.

BACKGROUND: Serrated polyps have recently been reported in patients with ulcerative colitis (UC); however, their prevalence and detailed characteristics remain unclear. METHODS: The prevalence and clinicopathological and biological characteristics of serrated polyps in patients with UC were retrospectively examined in a single tertiary inflammatory bowel disease center in Japan from 2000 to 2020. RESULTS: Among 2035 patients with UC who underwent total colonoscopy, 252 neoplasms, including 36 serrated polyps (26 in colitis-affected segments, 10 in colitis-unaffected segments), were identified in 187 patients with UC. The proportion of serrated polyps was 1.8% (36/2035). Serrated polyps in colitis-affected segments were common with extensive colitis (88%), history of persistent active colitis (58%), and long UC duration (12.1 years). Serrated polyps in colitis-affected segments were more common in men (88%). Of the 26 serrated polyps in colitis-affected segments, 15, 6, and 5 were categorized as sessile serrated lesion-like dysplasia, traditional serrated adenoma-like dysplasia, and serrated dysplasia not otherwise specified, respectively. Sessile serrated lesion-like dysplasia was common in the proximal colon (67%) and with BRAF mutation (62%), whereas traditional serrated adenoma-like dysplasia and serrated dysplasia not otherwise specified were common in the distal colon (100% and 80%, respectively) and with KRAS mutations (100% and 75%, respectively). CONCLUSIONS: Serrated polyps comprised 14% of the neoplasias in patients with UC. Serrated polyps in colitis-affected segments were common in men with extensive and longstanding colitis, suggesting chronic inflammation in the development of serrated polyps in patients with UC.

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.

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.

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.

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.

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.

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.

Adsorptive removal and photocatalytic decomposition of cationic dyes on niobium oxide with deformed orthorhombic structure.

Nano-rod-shaped niobium oxide with a deformed orthorhombic structure (ortho-Nb2O5) is first demonstrated as a selective adsorbent to remove cationic dyes wastewater. Ortho-Nb2O5 quickly adsorbs methylene blue (MB) with much greater capacity than reported inorganic adsorbents. Furthermore, ortho-Nb2O5 has a stronger affinity to cationic dye than anionic dye because cation exchange is involved in the adsorption process. The dye molecule adsorbed onto ortho-Nb2O5 can be degraded entirely under UV light irradiation because of its photocatalytic properties. Moreover, the regenerated ortho-Nb2O5 shows high reusability for use in additional adsorption processing. As described herein, new insights into the use of ortho-Nb2O5 as a photocatalytically regeneratable adsorbent for wastewater treatment are presented.

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 oxide-based membranes for pervaporative desalination of concentrated brines.

An all-inorganic zeolitic octahedral metal oxide based on cobalt tungstoselenate with porosity and hydrophilicity is successfully used to fabricate a membrane. The as-synthesized membrane and its ion-exchanged membranes exhibit extraordinary permeation flux with high salt rejection by pervaporative desalination for high-salinity brines up to 25 wt%.

Bulk tungsten-substituted vanadium oxide for low-temperature NOx removal in the presence of water.

NH3-SCR (selective catalytic reduction) is important process for removal of NOx. However, water vapor included in exhaust gases critically inhibits the reaction in a low temperature range. Here, we report bulk W-substituted vanadium oxide catalysts for NH3-SCR at a low temperature (100-150 °C) and in the presence of water (~20 vol%). The 3.5 mol% W-substituted vanadium oxide shows >99% (dry) and ~93% (wet, 5-20 vol% water) NO conversion at 150 °C (250 ppm NO, 250 ppm NH3, 4% O2, SV = 40000 mL h-1 gcat-1). Lewis acid sites of W-substituted vanadium oxide are converted to Brønsted acid sites under a wet condition while the distribution of Brønsted and Lewis acid sites does not change without tungsten. NH4+ species adsorbed on Brønsted acid sites react with NO accompanied by the reduction of V5+ sites at 150 °C. The high redox ability and reactivity of Brønsted acid sites are observed for bulk W-substituted vanadium oxide at a low temperature in the presence of water, and thus the catalytic cycle is less affected by water vapor.

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 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.

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.

Zeolitic Vanadomolybdates as High-Performance Cathode-Active Materials for Sodium-Ion Batteries.

Developing new cathode-active materials for rechargeable batteries is important to fulfill the growing demands of energy transformation, storage, and utilization. Zeolitic transition-metal oxides based on vanadomolybdate, constructed by pentagon metal-oxygen clusters as building blocks and metal ions as linkers in a trigonal symmetry, are good candidates for cathodes of Na rechargeable batteries. The material is activated via amorphization of the crystal structure in the ab plane during discharging process, keeping the molecular structure of the building blocks stable, which causes high specific capacity and good cycle performance.