Superionic conduction in a Mg-containing covalent organic framework at intermediate temperature.

We report superionic conduction in a Mg-containing covalent organic framework (COF) at intermediate temperature in the absence of guest vapors. A COF containing Mg carriers and polyethylene oxide (PEO) chains in its channels (TPB-PEO-9-COF-Mg) was synthesized. TPB-PEO-9-COF-Mg showed superionic conductivity above 10 S cm under dry N at 160 °C.

High ionic conduction in a robust anionic metal-organic framework containing Mg under guest vapors.

We report on the synthesis and high ionic conductivity of a highly crystalline Mg-containing metal-organic framework (MOF) with Type A feature (, anionic framework having Mg as a counter cation). We synthesized Mg[Zr(CHO)] (SU-102-Mg) through ion exchange reaction. SU-102-Mg showed a high ionic conductivity of 3.

(2,2')-1,1'-([1,1'-Biphen-yl]-4,4'-di-yl)bis-[3-(di-meth-yl-amino)-prop-2-en-1-one].

The title compound, CHNO, crystallizes in space group 2/. The mol-ecular structure is almost planar except for a tilt of the phenyl rings. The allyl groups on both ends exhibit the -form and the connected N atoms show character.

Ethidium benzoate methanol monosolvate.

In the title salt solvate (systematic name: 8-amino-5-ethyl-6-phenyl-phenanthridin-5-ium benzoate methanol monosolvate), CHN ·CHCO ·CHOH, two ethidium cations, CHN , dimerize about a twofold axis through π-π inter-actions [inter-centroid separation = 3.6137 (4) Å]. The benzoate anions are connected through hydrogen bonding with the -NH groups of the ethidium cations and the -OH group of the MeOH mol-ecule.

Design of a robust and strong-acid MOF platform for selective ammonium recovery and proton conductivity.

Metal-organic frameworks (MOFs) are potential candidates for the platform of the solid acid; however, no MOF has been reported that has both aqueous ammonium stability and a strong acid site. This manuscript reports a highly stable MOF with a cation exchange site synthesized by the reaction between zirconium and mellitic acid under a high concentration of ammonium cations (NH). Single-crystal XRD analysis of the MOF revealed the presence of four free carboxyl groups of the mellitic acid ligand, and the high first association constant (p) of one of the carboxyl groups acts as a monovalent ion-exchanging site.

High Mg conduction in three-dimensional pores of a metal-organic framework under organic vapors.

We report on high Mg conduction in a metal-organic framework (MOF), UiO-66, under organic vapors. We prepared a Mg-containing MOF, UiO-66⊃{Mg(TFSI)} (TFSI = bis(trifluoromethanesulfonyl)imide), including Mg carriers in three-dimensional pores. The compound showed a superionic conductivity above 10 S cm under MeCN and MeOH vapors.

Ethidium tetra-phenyl-borate aceto-nitrile disolvate.

In the title solvated salt, (CHN){B(CH)}·2CHCN (systematic name 3,8-di-amino-5-ethyl-6-phenyl-phenanthridin-5-ium tetra-phenyl-borate aceto-nitrile disolvate), the dihedral angle between the tricyclic fused ring system (r.m.s.

Ethidium hepta-fluoro-butyrate.

In the title compound (systematic name: 3,8-diamino-5-ethyl-6-phenylphenanthridin-5-ium 2,2,3,3,4,4,4-heptafluorobutyrate), CHN ·CFO , two ethidium ions, CHN form a dimerized structure due to π-π inter-actions, even though they are positively charged. The hepta-fluoro-butyrate anions are connected to neighbouring cation dimers hydrogen-bonding inter-actions, the hydrogen-bonding donor sites of the -NH groups of the ethidium ions connecting to the hydrogen-bonding acceptor sites of the -COO groups of the hepta-fluoro-butyrate anions.

Preparation of a Mg-containing MOF through ion exchange and its high ionic conductivity.

We report, for the first time, the preparation and ionic conductivity of a Mg-containing metal-organic framework (MOF) having type A features, , an anionic framework containing Mg as the counter cation. We prepared Mg[(MnMoO)L] (L = C{CHCHNC(CHO)}) (MOF-688-Mg) through a simple ion exchange reaction, and it showed high ionic conductivity above 10 S cm at 25 °C under MeCN vapor.

Super Mg Conductivity around 10 S cm Observed in a Porous Metal-Organic Framework.

We first report a solid-state crystalline "Mg conductor" showing a superionic conductivity of around 10 S cm at ambient temperature, which was obtained using the pores of a metal-organic framework (MOF), MIL-101, as ion-conducting pathways. The MOF, MIL-101⊃{Mg(TFSI)} (TFSI = bis(trifluoromethanesulfonyl)imide), containing Mg inside its pores, showed a superionic conductivity of 1.9 × 10 S cm at room temperature (RT) (25 °C) under the optimal guest vapor (MeCN), which is the highest value among all Mg-containing crystalline compounds.

Support effects of metal-organic frameworks in heterogeneous catalysis.

Catalytic support effects have been widely studied as a key factor for creating highly active heterogeneous catalysts with limited amounts of rare metal elements. Recently, support effects of metal-organic frameworks (MOFs) started to be investigated using their wide variety in pore size, electronic state, and selective adsorption property. Three types of support effects, namely molecular sieving, charge transfer, and substrate adsorption effects, have been reported on composite catalysts of metal nanoparticles supported on MOFs (M/MOFs).

Ion-conductive metal-organic frameworks.

Metal-organic frameworks (MOFs) have emerged as a new class of ionic conductors because of their tuneable and highly ordered microporous structures. The ionic conduction of various ionic carriers, such as a proton (H), hydroxide ion (OH), lithium ion (Li), sodium ion (Na), and magnesium ion (Mg), in the pores of MOFs has been widely investigated over the past decade. Reports reveal that the porous or channel structures of MOFs are fundamentally suitable as ion-conducting pathways.

Support Effect of Metal-Organic Frameworks on Ethanol Production through Acetic Acid Hydrogenation.

We present a systematic study on the support effect of metal-organic frameworks (MOFs), regarding substrate adsorption. A remarkable enhancement of both catalytic activity and selectivity for the ethanol (EtOH) production reaction through acetic acid (AcOH) hydrogenation (AH) was observed on Pt nanoparticles supported on MOFs. The systematic study on catalysis using homogeneously loaded Pt catalysts, in direct contact with seven different MOF supports (MIL-125-NH, UiO-66-NH, HKUST-1, MIL-101, Zn-MOF-74, Mg-MOF-74, and MIL-121) (abbreviated as ), found that MOFs having a high affinity for the AcOH substrate (UiO-66-NH and MIL-125-NH) showed high catalytic activity for AH.

Electrochemical hydrogenation of non-aromatic carboxylic acid derivatives as a sustainable synthesis process: from catalyst design to device construction.

Electrochemical hydrogenation of a carboxylic acid using water as a hydrogen source is an environmentally friendly synthetic process for upgrading bio-based chemicals. We systematically studied electrochemical hydrogenation of non-aromatic carboxylic acid derivatives on anatase TiO2 by a combination of experimental analyses and density functional theory calculations, which for the first time shed light on mechanistic insights for the electrochemical hydrogenation of carboxylic acids. Development of a substrate permeable TiO2 cathode enabled construction of a flow-type electrolyser, i.

Tailoring widely used ammonia synthesis catalysts for H and N poisoning resistance.

Despite many advancements, an inexpensive ammonia synthesis catalyst free from hydrogen and nitrogen poisoning, and capable of synthesizing ammonia under mild conditions is still unknown and is long sought-after. Here we present an active nanoalloy catalyst, RuFe, formed by alloying highly active Ru and inexpensive Fe, capable of activating both N2 and H2 without blocking the surface active sites and thereby overcoming the major hurdle faced by the current best performing pure metal catalysts. This novel RuFe nanoalloy catalyst operates under milder conditions than the conventional Fe catalyst and is less expensive than the so far best performing Ru-based catalysts providing additional advantages.

Proton transfer in hydrogen-bonded degenerate systems of water and ammonia in metal-organic frameworks.

Porous crystalline metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) are emerging as a new class of proton conductors with numerous investigations. Some of the MOFs exhibit an excellent proton-conducting performance (higher than 10 S cm) originating from the interesting hydrogen(H)-bonding networks with guest molecules, where the conducting medium plays a crucial role. In the overwhelming majority of MOFs, the conducting medium is HO because of its degenerate conjugate acid-base system (H3O + HO ⇔ HO + HO or OH + HO ⇔ HO + OH) and the efficient H-bonding ability through two proton donor and two acceptor sites with a tetrahedral geometry.

Consecutive oxidative additions of iodine on undulating 2D coordination polymers: formation of I-Pt-I chains and inhomogeneous layers.

The 2D coordination polymers, [Mn(salen)]2[PtII(CN)4]1-x[PtIV(CN)4(I2)]x (salen = N,N'-ethylenebis(salicylideneaminato), x = 0.18 (1), 0.45 (2), 0.

Electrochemical Production of Glycolic Acid from Oxalic Acid Using a Polymer Electrolyte Alcohol Electrosynthesis Cell Containing a Porous TiO Catalyst.

A liquid flow-type electrolyser that continuously produces an alcohol from a carboxylic acid was constructed by employing a polymer electrolyte, named a polymer electrolyte alcohol electrosynthesis cell (PEAEC). Glycolic acid (GC, an alcoholic compound) is generated on anatase TiO catalysts via four-electron reduction of oxalic acid (OX, a divalent carboxylic acid), accompanied with water oxidation, which achieves continuous electric power storage in easily stored GC. Porous anatase TiO directly grown on Ti mesh (TiO/Ti-M) or Ti felt (TiO/Ti-F) was newly fabricated as a cathode having favourable substrate diffusivity.

Modulation of the catalytic activity of Pt nanoparticles through charge-transfer interactions with metal-organic frameworks.

We employed metal-organic framework (MOF) supports to modulate the electronic states of loaded Pt nanoparticles (NPs) in their composite catalysts (Pt/MOFs). Pt NPs were homogenously deposited on four MOFs characterized with different electronic states (Zn-MOF-74, Mg-MOF-74, HKUST-1, and UiO-66-NH). Theoretical and experimental studies demonstrated that a charge-transfer interaction between Pt NPs and MOFs is a critical factor for controlling the catalytic activity of Pt NPs supported on MOFs.

Electroreduction of Carbon Dioxide to Hydrocarbons Using Bimetallic Cu-Pd Catalysts with Different Mixing Patterns.

Electrochemical conversion of CO holds promise for utilization of CO as a carbon feedstock and for storage of intermittent renewable energy. Presently Cu is the only metallic electrocatalyst known to reduce CO to appreciable amounts of hydrocarbons, but often a wide range of products such as CO, HCOO, and H are formed as well. Better catalysts that exhibit high activity and especially high selectivity for specific products are needed.

Hydrated Proton-Conductive Metal-Organic Frameworks.

Recent investigations into proton conduction in metal-organic frameworks (MOFs) indicate that MOFs are promising materials as a new class of proton conductors. Hydrated proton-conductive MOFs show not only high proton conductivity of approximately 10  S cm , which is comparable to that of a practical organic polymer, but also structural visibility of proton-conducting pathways inside the materials owing to their high crystallinity. Herein, studies on the design, synthesis, and proton-conductive properties of MOFs with hydrated proton-conductive systems are introduced.

A new approach for the facile preparation of metal-organic framework composites directly contacting with metal nanoparticles through arc plasma deposition.

The arc plasma deposition (APD) method is first applied to prepare metal-organic framework (MOF) composites loading metal nanoparticles having a direct contact with the MOF. We demonstrate the detailed growth mechanism of metal particles on the MOFs and the applicability of the APD for various combinations of metals and MOFs.

Superionic Conduction in Co-Vacant P2-Nax CoO2 Created by Hydrogen Reductive Elimination.

The layered P2-Nax MO2 (M: transition metal) system has been widely recognized as electronic or mixed conductor. Here, we demonstrate that Co vacancies in P2-Nax CoO2 created by hydrogen reductive elimination lead to an ionic conductivity of 0.045 S cm(-1) at 25 °C.