Super Mg2+ Conductivity around 10-3 S cm-1 Observed in a Porous Metal-Organic Framework.

We first report a solid-state crystalline "Mg2+ conductor" showing a superionic conductivity of around 10-3 S cm-1 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)2}1.6 (TFSI- = bis(trifluoromethanesulfonyl)imide), containing Mg2+ inside its pores, showed a superionic conductivity of 1.9 × 10-3 S cm-1 at room temperature (RT) (25 °C) under the optimal guest vapor (MeCN), which is the highest value among all Mg2+-containing crystalline compounds. The Mg2+ conductivity in the MOF was estimated to be 0.8 × 10-3 S cm-1 at RT, by determining the transport number of Mg2+ (tMg2+ = 0.41), which is the level as high as practical use for secondary battery. Measurements of adsorption isotherms, pressure dependence of ionic conductivity, and in situ Fourier transform infrared measurements revealed that the "super Mg2+ conductivity" is caused by the efficient migration of the Mg2+ carrier with the help of adsorbed guest molecules.

Flexibility Control of Two-Dimensional Coordination Polymers by Crystal Morphology: Water Adsorption and Thermal Expansion.

Layer flexibility in two-dimensional coordination polymers (2D-CPs) contributes to several functional materials as it results in anisotropic structural response to external stimuli. Chemical modification is a common technique for modifying layer structures. This study demonstrates that crystal morphology of a cyanide-bridged 2D-CP of type [Mn(salen)]2 [ReN(CN)4 ] (1) consisting of flexible undulating layers significantly impacts the layer configuration and assembly. Nanoplates of 1 showed an in-plane contraction of layers with a longer interlayer distance compared to the micrometer-sized rod-type particles. These effects by crystal morphology on the structure of the 2D-CP impacted the structural flexibility, resulting in dual-functional changes: the enhancement of the sensitivity of structural transformation to water adsorption and modification of anisotropic thermal expansion of 1. Moreover, the nanoplates incorporated new adsorption sites within the layers, resulting in the uptake of an additional water molecule compared to the micrometer-sized rods.

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.e., a so-called polymer electrode alcohol synthesis cell (PEAEC) for the continuous synthesis of an alcoholic compound from a carboxylic acid. We demonstrated the highly efficient and selective conversion of oxalic acid to produce glycolic acid, which can be regarded as direct electric power storage into an easily treatable alcoholic compound.

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. Most importantly, by integrating theory and experiments, we identified the underlying mechanisms responsible for lower surface poisoning of this catalyst, which will provide directions for fabricating poison-free efficient NH3 synthesis catalysts in future.

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

Electrochemical conversion of CO2 holds promise for utilization of CO2 as a carbon feedstock and for storage of intermittent renewable energy. Presently Cu is the only metallic electrocatalyst known to reduce CO2 to appreciable amounts of hydrocarbons, but often a wide range of products such as CO, HCOO-, and H2 are formed as well. Better catalysts that exhibit high activity and especially high selectivity for specific products are needed. Here a range of bimetallic Cu-Pd catalysts with ordered, disordered, and phase-separated atomic arrangements (Cuat:Pdat = 1:1), as well as two additional disordered arrangements (Cu3Pd and CuPd3 with Cuat:Pdat = 3:1 and 1:3), are studied to determine key factors needed to achieve high selectivity for C1 or C2 chemicals in CO2 reduction. When compared with the disordered and phase-separated CuPd catalysts, the ordered CuPd catalyst exhibits the highest selectivity for C1 products (>80%). The phase-separated CuPd and Cu3Pd achieve higher selectivity (>60%) for C2 chemicals than CuPd3 and ordered CuPd, which suggests that the probability of dimerization of C1 intermediates is higher on surfaces with neighboring Cu atoms. Based on surface valence band spectra, geometric effects rather than electronic effects seem to be key in determining the selectivity of bimetallic Cu-Pd catalysts. These results imply that selectivities to different products can be tuned by geometric arrangements. This insight may benefit the design of catalytic surfaces that further improve activity and selectivity for CO2 reduction.

Proton Conduction Study on Water Confined in Channel or Layer Networks of La(III)M(III)(ox)3·10H2O (M = Cr, Co, Ru, La).

Proton conduction of the La(III)M(III) compounds, LaM(ox)3·10H2O (abbreviated to LaM; M = Cr, Co, Ru, La; ox(2-) = oxalate) is studied in view of their networks. LaCr and LaCo have a ladder structure, and the ladders are woven to form a channel network. LaRu and LaLa have a honeycomb sheet structure, and the sheets are combined to form a layer network. The occurrence of these structures is explained by the rigidness versus flexibility of [M(ox)3](3-) in the framework with large La(III). The channel networks of LaCr and LaCo show a remarkably high proton conductivity, in the range from 1 × 10(-6) to 1 × 10(-5) S cm(-1) over 40-95% relative humidity (RH) at 298 K, whereas the layer networks of LaCr and LaCo show a lower proton conductivity, ∼3 × 10(-8) S cm(-1) (40-95% RH, 298 K). Activation energy measurements demonstrate that the channels filled with water molecules serve as efficient pathways for proton transport. LaCo was gradually converted to La(III)Co(II)(ox)2.5·4H2O, which had no channel structure and exhibited a low proton conductivity of less than 1 × 10(-10) S cm(-1). The conduction-network correlation of LaCo(ox)2.5·4H2O is reported.

Atomically mixed Fe-group nanoalloys: catalyst design for the selective electrooxidation of ethylene glycol to oxalic acid.

We demonstrate electric power generation via the electrooxidation of ethylene glycol (EG) on a series of Fe-group nanoalloy (NA) catalysts in alkaline media. A series of Fe-group binary NA catalysts supported on carbon (FeCo/C, FeNi/C, and CoNi/C) and monometallic analogues (Fe/C, Co/C, and Ni/C) were synthesized. Catalytic activities and product distributions on the prepared Fe-group NA catalysts in the EG electrooxidation were investigated by cyclic voltammetry and chronoamperometry, and compared with those of the previously reported FeCoNi/C, which clarified the contributory factors of the metal components for the EG electrooxidation activity, C2 product selectivity, and catalyst durability. The Co-containing catalysts, such as Co/C, FeCo/C, and FeCoNi/C, exhibit relatively high catalytic activities for EG electrooxidation, whereas the catalytic performances of Ni-containing catalysts are relatively low. However, we found that the inclusion of Ni is a requisite for the prevention of rapid degradation due to surface modification of the catalyst. Notably, FeCoNi/C shows the highest selectivity for oxalic acid production without CO2 generation at 0.4 V vs. the reversible hydrogen electrode (RHE), resulting from the synergetic contribution of all of the component elements. Finally, we performed power generation using the direct EG alkaline fuel cell in the presence of the Fe-group catalysts. The power density obtained on each catalyst directly reflected the catalytic performances elucidated in the electrochemical experiments for the corresponding catalyst. The catalytic roles and alloying effects disclosed herein provide information on the design of highly efficient electrocatalysts containing Fe-group metals.

Proton conductivity control by ion substitution in a highly proton-conductive metal-organic framework.

Proton conductivity through two-dimensional (2-D) hydrogen-bonding networks within a layered metal-organic framework (MOF) (NH4)2(H2adp)[Zn2(ox)3]·3H2O (H2adp = adipic acid; ox = oxalate) has been successfully controlled by cation substitution. We synthesized a cation-substituted MOF, K2(H2adp)[Zn2(ox)3]·3H2O, where the ammonium ions in a well-defined hydrogen-bonding network are substituted with non-hydrogen-bonding potassium ions, without any apparent change in the crystal structure. We successfully controlled the proton conductivity by cleavage of the hydrogen bonds in a proton-conducting pathway, showing that the 2-D hydrogen-bonding networks in the MOF truly contribute to the high proton conductivity. This is the first example of the control of proton conductivity by ion substitution in a well-defined hydrogen-bonding network within a MOF.

Design and synthesis of hydroxide ion-conductive metal-organic frameworks based on salt inclusion.

We demonstrate a metal-organic framework (MOF) design for the inclusion of hydroxide ions. Salt inclusion method was applied to an alkaline-stable ZIF-8 (ZIF = zeolitic imidazolate framework) to introduce alkylammonium hydroxides as ionic carriers. We found that tetrabutylammonium salts are immobilized inside the pores by a hydrophobic interaction between the alkyl groups of the salt and the framework, which significantly increases the hydrophilicity of ZIF-8. Furthermore, ZIF-8 including the salt exhibited a capacity for OH(-) ion exchange, implying that freely exchangeable OH(-) ions are present in the MOF. ZIF-8 containing OH(-) ions showed an ionic conductivity of 2.3 × 10(-8) S cm(-1) at 25 °C, which is 4 orders of magnitude higher than that of the blank ZIF-8. This is the first example of an MOF-based hydroxide ion conductor.

Control of crystalline proton-conducting pathways by water-induced transformations of hydrogen-bonding networks in a metal-organic framework.

Structure-defined metal-organic frameworks (MOFs) are of interest because rational design and construction allow us to develop good proton conductors or possibly control the proton conductivity in solids. We prepared a highly proton-conductive MOF (NH4)2(adp)[Zn2(ox)3]·nH2O (abbreviated to 1·nH2O, adp: adipic acid, ox: oxalate, n = 0, 2, 3) having definite crystal structures and showing reversible structural transformations among the anhydrate (1), dihydrate (1·2H2O), and trihydrate (1·3H2O) phases. The crystal structures of all of these phases were determined by X-ray crystallography. Hydrogen-bonding networks consisting of ammonium ions, water molecules, and carboxylic acid groups of the adipic acids were formed inside the two-dimensional interlayer space in hydrated 1·2H2O and 1·3H2O. The crystal system of 1 or 1·2H2O (P21/c, No. 14) was changed into that of 1·3H2O (P1̅, No. 2), depending on water content because of rearrangement of guests and acidic molecules. Water molecules play a key role in proton conduction as conducting media and serve as triggers to change the proton conductivity through reforming hydrogen-bonding networks by water adsorption/desorption processes. Proton conductivity was consecutively controlled in the range from ∼10(-12) S cm(-1) (1) to ∼10(-2) S cm(-1) (1·3H2O) by the humidity. The relationships among the structures of conducting pathways, adsorption behavior, and proton conductivity were investigated. To the best of our knowledge, this is the first example of the control of a crystalline proton-conducting pathway by guest adsorption/desorption to control proton conductivity using MOFs.

Proton dynamics of two-dimensional oxalate-bridged coordination polymers.

A two-dimensional porous coordination polymer (NH4)2{HOOC(CH2)4COOH}[Zn2(C2O4)3] (abbreviated as (NH4)2(adp)[Zn2(ox)3] (adp = adipic acid, ox = oxalate)), which accommodates water molecules between the [Zn2(ox)3] layers, is highly remarked as a new type of crystalline proton conductor. In order to investigate its phase behavior and the proton conducting mechanism, we have performed adiabatic calorimetry, neutron diffraction, and quasi-elastic neutron scattering experiments on a fully hydrated sample (NH4)2(adp)[Zn2(ox)3]·3H2O with the highest proton conductivity (8 × 10(-3) S cm(-1), 25 °C, 98% RH). Its isostructural derivative K2(adp)[Zn2(ox)3]·3H2O was also measured to investigate the role of ammonium ions. (NH4)2(adp)[Zn2(ox)3]·3H2O and K2(adp)[Zn2(ox)3]·3H2O exhibit higher order transitions at 86 K and 138 K, respectively. From the magnitude of the transition entropy, the former is of an order-disorder type while the latter is of a displacive type. (NH4)2(adp)[Zn2(ox)3]·3H2O has four Debye-type relaxations and K2(adp)[Zn2(ox)3]·3H2O has two similar relaxations above each transition temperature. The two relaxations of (NH4)2(adp)[Zn2(ox)3]·3H2O with very small activation energies (ΔEa < 5 kJ mol(-1)) are due to the rotational motions of ammonium ions and play important roles in the proton conduction mechanism. It was also found that the protons in (NH4)2(adp)[Zn2(ox)3]·3H2O are carried through a Grotthuss mechanism. We present a discussion on the proton conducting mechanism based on the present structural and dynamical information.

Ethidium benzoate methanol monosolvate.

In the title salt solvate (systematic name: 8-amino-5-ethyl-6-phenyl-phenanthridin-5-ium benzoate methanol monosolvate), C21H20N3 +·C6H5CO2 -·CH3OH, two ethidium cations, C21H20N3 +, 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 -NH2 groups of the ethidium cations and the -OH group of the MeOH mol-ecule. The MeOH mol-ecule also accepts a hydrogen bond from the -NH2 group of the ethidium cation. The result is a one-dimensional hydrogen-bonded chain along the b-axis direction.

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

The title compound, C22H24N2O2, crystallizes in space group P21/n. The mol-ecular structure is almost planar except for a tilt of the phenyl rings. The allyl groups on both ends exhibit the trans-form and the connected N atoms show sp 2 character. The mol-ecules are stacked and assembled along the c-axis direction by C-H⋯π inter-actions.

Superionic conduction in a Mg2+-containing covalent organic framework at intermediate temperature.

We report superionic conduction in a Mg2+-containing covalent organic framework (COF) at intermediate temperature in the absence of guest vapors. A COF containing Mg2+ 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 10-4 S cm-1 under dry N2 at 160 °C.

A novel threefold interpenetrated zirconium metal-organic framework exhibiting separation ability for strong acids.

We report on the synthesis and selective adsorption property of a novel threefold interpenetrated Zr-based metal-organic framework (MOF), [Zr12O8(OH)8(HCOO)15(BPT)3] (BPT3- = [1,1'-biphenyl]-3,4',5-tricarboxylate) (abbreviated as Zr-BPT). This MOF shows a high tolerance to acidic conditions and has permanent pores, the size of which (approx. <5.6 Å) is the smallest ever reported among porous Zr-based MOFs with high acid tolerance. Zr-BPT selectively adsorbs aryl acids due to its strong affinity for them and exhibits separation ability, even between strong acid molecules, such as sulfonic and phosphonic acids. This is the first demonstration of a MOF exhibiting selective adsorption and separation ability for strong acids.

High ionic conduction in a robust anionic metal-organic framework containing Mg2+ under guest vapors.

We report on the synthesis and high ionic conductivity of a highly crystalline Mg2+-containing metal-organic framework (MOF) with Type A feature (i.e., anionic framework having Mg2+ as a counter cation). We synthesized Mg[Zr(C14H3O8)2] (SU-102-Mg) through ion exchange reaction. SU-102-Mg showed a high ionic conductivity of 3.6 × 10-5 S cm-1 (25 °C, under MeCN vapor).

Proton-conductive magnetic metal-organic frameworks, {NR3(CH2COOH)}[M(a)(II)M(b)(III)(ox)3]: effect of carboxyl residue upon proton conduction.

Proton-conductive magnetic metal-organic frameworks (MOFs), {NR(3)(CH(2)COOH)}[M(a)(II)M(b)(III)(ox)(3)] (abbreviated as R-M(a)M(b): R = ethyl (Et), n-butyl (Bu); M(a)M(b) = MnCr, FeCr, FeFe) have been studied. The following six MOFs were prepared: Et-MnCr·2H(2)O, Et-FeCr·2H(2)O, Et-FeFe·2H(2)O, Bu-MnCr, Bu-FeCr, and Bu-FeFe. The structure of Bu-MnCr was determined by X-ray crystallography. Crystal data: trigonal, R3c (#161), a = 9.3928(13) Å, c = 51.0080(13) Å, Z = 6. The crystal consists of oxalate-bridged bimetallic layers interleaved by {NBu(3)(CH(2)COOH)}(+) ions. Et-MnCr·2H(2)O and Bu-MnCr (R-MnCr MOFs) show a ferromagnetic ordering with T(C) of 5.5-5.9 K, and Et-FeCr·2H(2)O and Bu-FeCr (R-FeCr MOFs) also show a ferromagnetic ordering with T(C) of 11.0-11.5 K. Et-FeFe·2H(2)O and Bu-FeFe (R-FeFe MOFs) belong to the class II of mixed-valence compounds and show the magnetism characteristic of Néel N-type ferrimagnets. The Et-MOFs (Et-MnCr·2H(2)O, Et-FeCr·2H(2)O and Et-FeFe·2H(2)O) show high proton conduction, whereas the Bu-MOFs (Bu-MnCr, Bu-FeCr, and Bu-FeFe) show moderate proton conduction. Together with water adsorption isotherm studies, the significance of the carboxyl residues as proton carriers is revealed. The R-MnCr MOFs and the R-FeCr MOFs are rare examples of coexistent ferromagnetism and proton conduction, and the R-FeFe MOFs are the first examples of coexistent Néel N-type ferrimagnetism and proton conduction.

High Mg2+ conduction in three-dimensional pores of a metal-organic framework under organic vapors.

We report on high Mg2+ conduction in a metal-organic framework (MOF), UiO-66, under organic vapors. We prepared a Mg2+-containing MOF, UiO-66⊃{Mg(TFSI)2}1.0 (TFSI- = bis(trifluoromethanesulfonyl)imide), including Mg2+ carriers in three-dimensional pores. The compound showed a superionic conductivity above 10-4 S cm-1 under MeCN and MeOH vapors.

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 (NH4+). 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 (pKa1) of one of the carboxyl groups acts as a monovalent ion-exchanging site. NH4+ in the MOF can be reversibly exchanged with proton (H+), sodium (Na+), and potassium (K+) cations in an aqueous solution. Moreover, the uniform nanospace of the MOF provides the acid site for selective NH4+ recovery from the aqueous mixture of NH4+ and Na+, which could solve the global nitrogen cycle problem. The solid acid nature of the MOF also results in the proton conductivity reaching 1.34 × 10-3 S cm-1 at 55 °C by ion exchange from NH4+ to H+.

Promotion of low-humidity proton conduction by controlling hydrophilicity in layered metal-organic frameworks.

We controlled the hydrophilicity of metal-organic frameworks (MOFs) to achieve high proton conductivity and high adsorption of water under low humidity conditions, by employing novel class of MOFs, {NR(3)(CH(2)COOH)}[MCr(ox)(3)]·nH(2)O (abbreviated as R-MCr, where R = Me (methyl), Et (ethyl), or Bu (n-butyl), and M = Mn or Fe): Me-FeCr, Et-MnCr, Bu-MnCr, and Bu-FeCr. The cationic components have a carboxyl group that functions as the proton carrier. The hydrophilicity of the cationic ions was tuned by the NR(3) residue to decrease with increasing bulkiness of the residue: {NMe(3)(CH(2)COOH)}(+) > {NEt(3)(CH(2)COOH)}(+) > {NBu(3)(CH(2)COOH)}(+). The proton conduction of the MOFs increased with increasing hydrophilicity of the cationic ions. The most hydrophilic sample, Me-FeCr, adsorbed a large number of water molecules and showed a high proton conductivity of ~10(-4) S cm(-1), even at a low humidity of 65% relative humidity (RH), at ambient temperature. Notably, this is the highest conductivity among the previously reported proton-conducting MOFs that operate under low RH conditions.