High-Valence Metal Doping Induced Lattice Expansion for M-FeNi LDH toward Enhanced Urea Oxidation Electrocatalytic Activities.

The precise design of low-cost, efficient, and definite electrocatalysts is the key to sustainable renewable energy. The urea oxidation reaction (UOR) offers a promising alternative to the oxygen evolution reaction for energy-saving hydrogen generation. In this study, by tuning the lattice expansion, a series of M-FeNi layered double hydroxides (M-FeNi LDHs, M: Mo, Mn, V) with excellent UOR performance are synthesized.

Rational regulation of acetylene adsorption and separation for ultra-microporous copper-1,2,4-triazolate frameworks by halogen hydrogen bonds.

It is well known that the introduction of exposed fluorine (F) sites into metal-organic frameworks (MOFs) can effectively promote acetylene (CH) adsorption C-H⋯F hydrogen bonds. However, such super strong hydrogen bonding interactions usually lead to very high acetylene adsorption enthalpy and thus require more energy during the adsorbent regeneration process. As the same group elements, chlorine (Cl), bromine (Br) and iodine (I) also can act as hydrogen bond acceptors but with relatively weak forces.

Micropore Regulation in Ultrastable [ScO]-Organic Frameworks for Acetylene Storage and Purification.

High storage capacity, high separation selectivity, and high structure stability are essential for an idea gas adsorbent. However, it is not easy to achieve all three at the same time, even for the promising metal-organic framework (MOF) adsorbents. We demonstrate herein that robust [ScO]-organic frameworks could be regulated by a micropore combination strategy for high-performance acetylene adsorption.

Cobalt phosphide nanorings towards efficient electrocatalytic nitrate reduction to ammonia.

High-quality CoP nanorings (CoP NRs) are easily achieved using a phosphorating treatment of CoOOH nanorings, and reveal high activity towards the hydrogen evolution reaction and the nitrate electrocatalytic reduction reaction due to substantial coordinately unsaturated active sites, a high surface area, and available mass transfer pathways. Consequently, the CoP NRs can achieve a faradaic efficiency of 97.1% towards NO-to-NH conversion and provide an NH yield of 30.

Ultrahigh-Uptake Capacity-Enabled Gas Separation and Fruit Preservation by a New Single-Walled Nickel-Organic Framework.

High gas-uptake capacity is desirable for many reasons such as gas storage and sequestration. Moreover, ultrahigh capacity can enable a practical separation process by mitigating the selectivity factor that sometimes compromises separation efficiency. Herein, a single-walled nickel-organic framework with an exceptionally high gas capture capability is reported.

Precise Pore Space Partitions Combined with High-Density Hydrogen-Bonding Acceptors within Metal-Organic Frameworks for Highly Efficient Acetylene Storage and Separation.

The high storage capacity versus high selectivity trade-off barrier presents a daunting challenge to practical application as an acetylene (C H ) adsorbent. A structure-performance relationship screening for sixty-two high-performance metal-organic framework adsorbents reveals that a moderate pore size distribution around 5.0-7.

Tuning the Pore Surface of an Ultramicroporous Framework for Enhanced Methane and Acetylene Purification Performance.

Both methane (CH) and acetylene (CH) are important energy source and raw chemicals in many industrial processes. The development of an energy-efficient and environmentally friendly separation and purification strategy for CH and CH is necessary. Ultramicroporous metal-organic framework (MOF) materials have shown great success in the separation and purification of small-molecule gases.

Tailoring the Pore Environment of a Robust Ga-MOF by Deformed [GaO(COO)] Cluster for Boosting CH Uptake and Separation.

The construction of superstable metal-organic frameworks (MOFs) for selective gas uptake is urgently demanded but remains a great challenge. Herein, a unique bifunctional deformed [GaO(COO)] inorganic secondary building unit (SBU) generated from the desymmetrical evolution of typical triangular prismatic trinuclear cluster was first introduced, which was extended by an isosceles triangular organic linker to produce a robust Ga-MOF (). Remarkably, can stabilize in water at 25 °C for 96 h and at 80 °C for more than 24 h, which surpasses nearly all other Ga-MOFs.

Systematic Regulation of CH/CO Separation by 3p-Block Open Metal Sites in a Robust Metal-Organic Framework Platform.

The separation of a mixture of CH and CO is a great challenge due to their similar molecular sizes and shapes. Al-based metal-organic frameworks (Al-MOFs) have great promise for gas separation applications due to their light weight, high stability, and low cost. However, the cultivation of suitable Al-MOF single crystals is extremely difficult and has limited their explorations up to now.

Mimic of Ferroalloy To Develop a Bifunctional Fe-Organic Framework Platform for Enhanced Gas Sorption and Efficient Oxygen Evolution Electrocatalysis.

It is well-known that the formation of ferroalloy with the addition of the second or third metal during the steel-making process usually can improve the performance of the iron. Inspired by ferroalloy materials, it is speculated that the pore environment, framework charge, and catalytic properties of metal-organic frameworks (MOFs) could be optimized dramatically via the introduction of ferroalloy-like inorganic building blocks. However, different to ferroalloy, the accurate integration of different metals into one MOF platform is still challenging.

Topology-Guided Design for Sc-soc-MOFs and Their Enhanced Storage and Separation for CO and C-Hydrocarbons.

Evaluating the effect of ligand substitution on metal ions and/or clusters during the MOF growth process is conducive to rational design of isoreticular MOFs with improved performance. Through topological direction and ligand substitution strategy, we herein constructed two Sc-soc-MOFs ( and ) based on two similar rectangular-planar diisophthalate ligands, linear-shaped HEBTC (1,1'-ethynebenzene-3,3',5,5'-tetracarboxylic acid) and zigzag-shaped HABTC (3,3',5,5'-azobenzenetetracarboxylic acid), under solvothermal conditions with formic acid as a modulator. {Sc[(ScO)(HO)](EBTC)} () possesses two distinct clusters as SBUs, trinuclear [ScO(CO)] (SBU1) and mononuclear cluster [ScO] (SBU2), which maintain the soc-topology except for the mononuclear [ScO] instead of the corresponding trinuclear [ScO(CO)] in ({(ScO)(HO)(ABTC)(NO)}).

Ultramicroporous Building Units as a Path to Bi-microporous Metal-Organic Frameworks with High Acetylene Storage and Separation Performance.

A strategy called ultramicroporous building unit (UBU) is introduced. It allows the creation of hierarchical bi-porous features that work in tandem to enhance gas uptake capacity and separation. Smaller pores from UBUs promote selectivity, while larger inter-UBU packing pores increase uptake capacity.

Highly Selective and Sensitive Turn-Off-On Fluorescent Probes for Sensing Al Ions Designed by Regulating the Excited-State Intramolecular Proton Transfer Process in Metal-Organic Frameworks.

The concept of high-performance excited-state intramolecular proton transfer (ESIPT)-based fluorescent metal-organic framework (MOF) probes for Al is proposed in this work. By regulating the hydroxyl groups on the organic linker step by step, new fluorescent magnesium-organic framework (Mg-MOF) probes for Al ions were established based on the ESIPT fluorescence mechanism. It is observed for the first time that the number of intramolecular hydrogen bonds between adjacent hydroxyl and carboxyl groups can effectively adjust the ESIPT process and lead to tunable fluorescence sensing performance.

Design of High-Symmetrical Magnesium-Organic Frameworks with Acetate as Modulator and Their Fluorescence Sensing Performance.

During the formation of magnesium-organic frameworks, the coordination sphere of magnesium tends to be partially occupied by O-containing solvent molecules such as amides, which will dramatically decrease the symmetry of Mg-organic frameworks and thus lead to low stability. It is noted that up to now, most reported Mg-metal-organic frameworks (MOFs) (>80%) crystallize in the space groups whose symmetry is lower than that of a tetragonal system. In this work, we demonstrate that acetate (Ac) may act as modulator to eliminate the influence of amide solvent and improve the symmetry of Mg-organic frameworks.

A semiconductor and fluorescence dual-mode room-temperature ammonia sensor achieved by decorating hydroquinone into a metal-organic framework.

Presented herein is a magnesium-organic framework (SNNU-88) incorporated with active hydroquinone groups, which exhibits not only remarkable semiconductor sensing for traces of ammonia vapor (5-100 ppm), but also extra-high fluorescence response to liquid NH3·H2O through an unusual turn-off (0-1.5 ppm) and turn-on (3.0-100 ppm) luminescence sensing mechanism at room temperature.

Assembly of [Cu(COO)] and [M(μ-O)(COO)] (M = Sc, Fe, Ga, and In) building blocks into porous frameworks towards ultra-high CH/CO and CH/CH separation performance.

A porous MOF platform (SNNU-65s) formed by creatively combining paddle-wheel-like [Cu(COO)] and trigonal prismatic [M(μ-O)(COO)] building blocks was designed herein. The mixed and high-density open metal sites and the OH-functionalized pore surface promote SNNU-65s to exhibit ultra-high CH uptake and separation performance. Impressively, SNNU-65-Cu-Ga stands out for the highest CH/CO (18.

Atoms diffusion-induced phase engineering of platinum-gold alloy nanocrystals with high electrocatalytic performance for the formic acid oxidation reaction.

Bimetallic noble metal nanocrystals have been widely applied in many fields, which generally are synthesized by the wet-chemistry reduction method. This work presents a purposely designed atoms diffusion induced phase engineering of PtAu alloy nanocrystals on platy Au substrate (PtAu-on-Au nanostructures) through simple hydrothermal treatment. Benefitting from the synergistic effects of component and structure, PtAu-on-Au nanostructures remarkably enhance the dehydrogenation pathway of the formic acid oxidation reaction (FAOR), and thus exhibit much higher FAOR activity and durability compared with Pt nanocrystals on platy Au substrate (Pt-on-Au nanostructures) and commercial Pd black due to an excellent stability of platy Au substrate and a high oxidation resistance of PtAu alloy nanocrystals.

Ionothermal Design of Crystalline Halogeno(cyano)cuprate Family: Structure Diversity, Solid-State Luminescence, and Photocatalytic Performance.

A general preparative method for multifunctional halogeno(cyano)cuprate materials in ionic liquids is developed in this work. Under ionothermal conditions, alkylimidazolium-based ionic liquids serving as solvent, charge-compensating, and structure-directing agent, as well as reactant lead to 12 members of the novel hybrid halogeno(cyano)cuprate family with a general formula of [RRRIM][CuX(CN)] (RRRIM = alkylimidazolium cations, X = halide anions). X-ray single-crystal diffractions show that diverse inorganic halogeno(cyano)cuprate components vary from discrete complexes (1 and 2), one-dimensional (1D) chains (3-7), two-dimensional (2D) layer (8), to three-dimensional (3D) open frameworks (9-12).

Ionothermal synthesis of novel Pb-OH-Cu-X (X = Cl, Br and I) quaternary heterometallic frameworks with tunable optical properties.

Reported herein is the new application of ionothermal synthesis for inorganic optical materials. Under ionothermal conditions with different imidazolium ionic liquids, novel quaternary heterometallic frameworks based on [Pb(OH)] cubane and [CuCl] or [CuBr] chains and [CuI] binuclear clusters have been successfully produced. Simple chlorine, bromine and iodine replacement leads to not only the space group change (tetragonal I41/acd for 1 and 2, and orthorhombic Fddd for 3) but also the topological net transformation (8,12-net for 1 and 2, and 6,6-net for 3).

Ligand Torsion Triggered Two Robust Fe-Tetratopic Carboxylate Frameworks with Enhanced Gas Uptake and Separation Performance.

By regulating the tetratopic carboxylate ligands, two robust Fe-MOFs (MOF=Metal-organic framework) comprising trigonal prismatic building blocks under a DMA/DMSO/HBF solvent system, namely, [(CH ) NH ][Fe (OH)(BPTC) (DMSO) ] (SNNU-60) and [Fe Fe (OH)(ABTC) (DMSO) ] (SNNU-61) (BPTC=3,3',5,5'-biphenyltetracarboxylic acid, ABTC=3,3',5,5'-azobenzenetetracarboxylic acid, SNNU=Shaanxi Normal University) have been successfully synthesized. The torsions between the benzene groups of the ligands result in two MOFs exhibiting completely different (4,6)-connected frameworks, which represent the only two MOF types constructed by [M (O/OH)(COO) ] trimeric building units and quadrilateral tetratopic carboxylate linkers until now. The robust Fe-MOFs SNNU-60 and SNNU-61 both exhibit high thermal/chemical stability, permanent microporosity, and excellent gas uptake capability for H , CO , C H , and C H under 1 bar.

Microporous rod metal-organic frameworks with diverse Zn/Cd-triazolate ribbons as secondary building units for CO uptake and selective adsorption of hydrocarbons.

The synthetic design of new porous open-framework materials with pre-designed pore properties for desired applications such as gas adsorption and separation remains challenging. We proposed one such class of materials, rod metal-organic frameworks (rod MOFs), which can be tuned by using rod secondary building units (rod SBUs) with different geometrical and chemical features. Our approach takes advantage of the readily accessible metal-triazolate 1-D motifs as rod SBUs to combine with dicarboxylate ligands to prepare target rod MOFs.

Channel partition into nanoscale polyhedral cages of a triple-self-interpenetrated metal-organic framework with high CO2 uptake.

Reported herein is a novel porous metal-organic framework (MOF) exhibiting unique nanoscale cages derived from the 3-fold self-interpenetration of chiral eta networks based on trifurcate {Zn2(CO2)3} building blocks and 1,3,5-tris(4-carboxyphenyl)benzene ligands. The attractive self-interpenetrated structural features contribute to the highest CO2 uptake capacity and CO2 binding ability among the interpenetrated MOFs.

The first ionothermal synthesis of a 3D ferroelectric metal-organic framework with colossal dielectric constant.

A novel 3D (4,6)-connected topological architecture, obtained under ionothermal conditions by using 1-ethyl-3-methyl imidazolium bromide ([EMI]Br) as solvent and structure-directing agent, presents a non-centrosymmetric polar packing arrangement showing an interesting ferroelectric property.

A mixed-valence chair-like tetranuclear copper(I,II) cluster with three linking modes of the 3,5-bis(2-pyridyl)-1,2,4-triazole ligand.

In the tetranuclear copper complex tetrakis[mu-3,5-bis(2-pyridyl)-1,2,4-triazolido]bis[3,5-bis(2-pyridyl)-1,2,4-triazolido]dicopper(I)dicopper(II) dihydrate, [Cu(I)(2)Cu(II)(2)(C(12)H(8)N(5))(6)].2H(2)O, the asymmetric unit is composed of one Cu(I) center, one Cu(II) center, three anionic 3,5-bis(2-pyridyl)-1,2,4-triazole (2-BPT) ligands and one solvent water molecule. The Cu(I) and Cu(II) centers exhibit [Cu(I)N(4)] tetrahedral and [Cu(II)N(6)] octahedral coordination environments, respectively.