Trimetallic Ni-CuCoN Ohmic junction for the enhanced oxidation of methanol and urea.

Methanol oxidation reaction (MOR) and urea oxidation reaction (UOR) can be utilized as effective alternatives to the anodic oxygen evolution reaction (OER) in overall water-splitting. Nevertheless, the development of cost-effective, highly efficient and durable electrocatalysts for MOR and UOR remains a significant challenge. Herein, the Ohmic junction (Ni-CuCoN@CC) comprising CuCoN nanosheets and Ni nanoparticles anchored on carbon cloth (CC) was successfully synthesized via a two-step hydrothermal process followed by pyrolysis.

Defect-engineered indium-organic framework displays the higher CO adsorption and more excellent catalytic performance on the cycloaddition of CO with epoxides under mild conditions.

In order to achieve the high adsorption and catalytic performance of CO, the direct self-assembly of robust defect-engineered MOFs is a scarcely reported and challenging proposition. Herein, a highly robust nanoporous indium(III)-organic framework of {[In(CPPDA)(HO)](NO)·2DMF·3HO} (NUC-107) consisting of two kinds of inorganic units of chain-shaped [In(COO)(HO)] and watery binuclear [In(COO)(HO)] was generated by regulating the growth environment. It is worth mentioning that [In(COO)(HO)] is very rare in terms of its richer associated water molecules, implying that defect-enriched metal ions in the activated host framework can serve as strong Lewis acid.

Robust {Pb}-Cluster-Based Metal-Organic Framework for Capturing and Converting CO into Cyclic Carbonates under Mild Conditions.

Developing a highly active catalyst that can efficiently capture and convert carbon dioxide (CO) into high-value-added energy materials remains a severe challenge, which inspires us to explore effective metal-organic frameworks (MOFs) with high chemical stability and high-density active sites. Herein, we report a robust 3D lead(II)-organic framework of {(MeNH)[Pb(PTTPA)(HO)]·2DMF·3HO} () with unreported [Pb(COO)(HO)] clusters (abbreviated as {Pb}) as nodes (HPTTPA = 4,4',4″-(pyridine-2,4,6-triyl)triisophthalic acid). After thermal activation, is functionalized by the multifarious symbiotic acid-base active sites of open Pb sites and uncoordinated pyridine groups on the inner surface of the void volume.

Eu(III) functionalized ZnMOF based efficient dual-emission sensor integrated with self-calibrating logic gate for intelligent detection of epinephrine.

The rapid detection of epinephrine (EPI) in serum holds immense importance in the early disease diagnosis and regular monitoring. On the basis of the coordination post-synthetic modification (PSM) strategy, a Eu functionalized ZnMOF (Eu@ZnMOF) was fabricated by anchoring the Eu ions within the microchannels of ZnMOF as secondary luminescent centers. Benefiting from two independent luminescent centers, the prepared Eu@ZnMOF shows great potential as a multi-signal self-calibrating luminescent sensor in visually and efficiently detecting serum EPI levels, with high reliability, fast response time, excellentrecycleability, and low detection limits of 17.

Nanoporous {Co}-Organic framework for efficiently seperating gases and catalyzing cycloaddition of epoxides with CO and Knoevenagel condensation.

Enhancing the catalysis of metal-organic frameworks (MOFs) by regulating inherent Lewis acid-base sites to realize the efficient seperation and chemical fixation of inert carbon dioxide (CO) is crucial but challenging. Herein, the solvothermal self-assembly of Co, 5'-(4-carboxy-2-nitrophenyl)-2,2',2'',4',6'-pentanitro-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid (HTNBTB) and 4'-phenyl-4,2':6',4''-terpyridine (PTP) generated a highly robust cobalt-organic framework of {[Co(TNBTB)(PTP)]·7DMF·6HO} (NUC-82). In NUC-82, the tri-core clusters of {Co} with linear shape are bridged by TNBTB to form two-dimensional structure in ac plane, which is further linked by PTP to generate a three-dimensional framework with two kinds of solvent-accessible channels: rhombic-like (ca.

Robust Fluorine-Functionalized {Ln}-Organic Frameworks for Excellent Catalytic Performance on Cycloaddition of CO with Epoxides and Knoevenagel Condensation.

Lanthanide-organic frameworks (LnOFs) are a class of promising catalysts on a large number of organic reactions because of the higher coordination number of Ln ions, inspired by which exploratory preparation of cluster-based LnOFs was carried out by us. Herein, the exquisite combination of spindly [Ln(μ-OH)(CO)(HO)] clusters (abbreviated as {Ln}) and fluorine-functionalized tetratopic ligand of 2',3'-difluoro-[-terphenyl]-3,3″,5,5″-tetracarboxylic acid (F-HPTTA) engendered two highly robust isomorphic nanoporous frameworks of {[Ln(FPTTA)(μ-OH)(HO)](NO)} (, = and ). compounds are rarely reported {Ln}-based 3D frameworks with nano-caged voids (19 Å × 17 Å), which are shaped by twelve [Ln(μ-OH)(COO)] clusters and eight completely deprotonated F-PTTA ligands.

-[MoO]-based multifunctional hybrid material for high catalytic performance on the cycloaddition of CO, esterification and knoevenagel condensation.

Developing materials with excellent properties has become the norm in the field of basic research, prompting us to explore highly robust hybrid materials based on electron-rich POMs and electron-deficient MOFs. Herein, a -[MoO]-based hybrid material of [Cu(BPPP)]{-[MoO]} (NUC-62) with excellent physicochemical stability was self-assembled under acidic solvothermal conditions from NaMoO and CuCl in the presence of a designed chelated ligand of 1,3-bis(3-(2-pyridyl)pyrazol-1-yl)propane (BPPP), which has sufficient coordination sites, spatial self-regulation and great deformation ability. In NUC-62, each of two tetra-coordinated Cu ions and two BPPP are unified into one dinuclear unit serving as the cation, which is interactively linked to -[MoO] anions rich hydrogen bonds of C-H⋯O.

A highly robust cluster-based indium(III)-organic framework with efficient catalytic activity in cycloaddition of CO and Knoevenagel condensation.

The efficient catalytic performance displayed by MOFs is decided by an appropriate charge/radius ratio of defect metal sites, large enough solvent-accessible channels and Lewis base sites capable of polarizing substrate molecules. Herein, the solvothermal self-assembly led to a highly robust nanochannel-based framework of {[In(CPDD)(μ-OH)(DMF)(HO)]·2DMF·5HO} (NUC-66) with a 56.8% void volume, which is a combination of a tetranuclear cluster [In(μ-OH)(COO)(DMF)(HO)] (abbreviated as {In}) and a conjugated tetracyclic pentacarboxylic acid ligand of 4,4'-(4-(4-carboxyphenyl)pyridine-2,6-diyl)diisophthalic acid (HCPDD).

Highly Robust {In}-Organic Framework for Efficiently Catalyzing CO Cycloaddition and Knoevenagel Condensation.

To improve the catalytic performance of metal-organic frameworks (MOFs), creating higher defects is now considered as the most effective strategy, which can not only optimize the Lewis acidity of metal ions but also create more pore space to enhance diffusion and mass transfer in the channels. Herein, the exquisite combination of scarcely reported [In(CO)(HO)(DMF)] clusters and 2,6-bis(2,4-dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine (HBDCP) under solvothermal conditions generated a highly robust nanoporous framework of {[In(BDCP)(DMF)(HO)](NO)} () with nanocaged voids (14.1 Å) and rectangular nanochannels (15.

Eu(III)-Functionalized MOF-Based Dual-Emission Ratiometric Sensor Integrated with Logic Gate Operation for Efficient Detection of Hippuric Acid in Urine and Serum.

With the introduction of Eu ions as the secondary fluorescent signal reporter and sensing active sites, a dual-emission ratiometric sensor of (Eu functional ) for hippuric acid (HA) detection in urine and serum was fabricated the postsynthetic encapsulating strategy. Based on the two emission signals at 441 nm (turn-on) and 628 nm (turn-off), the produced ratiometric sensor provided enhanced sensitivity, higher selectivity, and 9.7 times lower limits of detection (LOD) for the detection of HA (2.

Nanocage-Based Tb-Organic Framework for Efficiently Catalyzing the Cycloaddition Reaction of CO with Epoxides and Knoevenagel Condensation.

The catalytic performance of metal-organic framework (MOF)-based catalysts can be enhanced by increasing their catalytic sites, which prompts us to explore the multicore cluster-based skeletons by using designed functional ligands. Herein, the exquisite combination of [Tb(μ-OH)(CO)] cluster and 2,6-bis(2,4-dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine (HBDCP) ligand generated a highly robust nanoporous framework of {[Tb(BDCP)(μ-OH)]·3DMF·5HO} (), in which each four {Tb} clusters are woven together to generate an elliptical nanocage (aperature ca. 12.

Fluorine-Functionalized NbO-Type {Cu}-Organic Framework: Enhanced Catalytic Performance on the Cycloaddition Reaction of CO with Epoxides and Deacetalization-Knoevenagel Condensation.

The high catalytic activity of metal-organic frameworks (MOFs) can be realized by increasing their effective active sites, which prompts us to perform the functionalization on selected linkers by introducing a strong Lewis basic group of fluorine. Herein, the exquisite combination of paddle-wheel [Cu(CO)(HO)] clusters and meticulously designed fluorine-funtionalized tetratopic 2',3'-difluoro-[-terphenyl]-3,3″,5,5″-tetracarboxylic acid (F-Hptta) engenders one peculiar nanocaged {Cu}-organic framework of {[Cu(F-ptta)(HO)]·5DMF·2HO} (), which features two types of nanocaged voids (9.8 Å × 17.

Nanochannel-based heterometallic {ZnHo}-organic framework with high catalytic activity for the chemical fixation of CO.

The exquisite combination of Zn and Ho generated the highly robust [ZnHo(CO)(OH)]-based heterometallic framework of {[ZnHo(TDP)(HO)]·5HO·3DMF} (NUC-30, HTDP = 2,4,6-tri(2',4'-dicarboxyphenyl)pyridine), which featured outstanding physicochemical properties, including honeycomb nanochannels, high porosity, large specific surface area, the coexistence of highly open Lewis acid-base sites, good thermal and chemical stability, and resistance to most organic solvents. Due to its extremely unsaturated metal tetra-coordinated Zn(ii) ions, hepta-coordinated Ho(iii) and high faveolate void volume (61.3%), the conversion rate of styrene oxide and CO into cyclic carbonates in the presence of 2 mol% activated NUC-30 and 5 mol% -BuNBr reached 99% under the mild conditions of 1.

Nanoporous {Y}-Organic Frameworks for Excellent Catalytic Performance on the Cycloaddition Reaction of Epoxides with CO and Deacetalization-Knoevenagel Condensation.

Stable metal-organic frameworks containing periodically arranged nanosized pores and active Lewis acid-base active sites are considered as ideal candidates for efficient heterogeneous catalysis. Herein, the exquisite combination of [Y(CO)(HO)] cluster (abbreviated as {Y}) and multifunctional linker of 2,4,6-tri(2,4-dicarboxyphenyl)pyridine (HTDP) led to a nanoporous framework of {[Y(TDP)(HO)]·5HO·4DMF} (, NUC = North University of China), which is a rarely reported binuclear three-dimensional (3D) framework with hierarchical tetragonal-microporous (0.78 nm) and octagonal-nanoporous (1.

Nanochannel-based {BaZn}-organic framework for catalytic activity on the cycloaddition reaction of epoxides with CO and deacetalization-Knoevenagel condensation.

Herein, the rare combination of Ba (5s) and Zn (3d) in the presence of the structure-oriented TDP ligand generated the nanochannel-based hybrid material {[(CH)NH][BaZn(TDP)(HO)]·DMF·5HO} (NUC-51, HTDP = 2,4,6-tri(2,4-dicarboxyphenyl)pyridine), which possesses excellent physicochemical characteristics such as nanoscopic channels, high porosity, large specific surface area, and high heat/water-resistance. To the best of our knowledge, this is the first 3D [BaZn(CO)(HO)]-based nano-porous host framework, whose activated state possesses the coexistence of Lewis acid-base sites including 4-coordinated Zn ions, 7-coordinated Ba ions, uncoordinated carboxyl oxygen atoms, and N atoms. Catalytic experiments exhibited that activated NUC-51a possesses a high catalytic activity on the cycloaddition reactions of epoxides with CO at 55 °C, which can be ascribed to its structural advantages of nanoscale channels and rich bifunctional active sites.

Investigation on the catalytic behavior of a novel thulium-organic framework with a planar tetranuclear {Tm} cluster as the active center for chemical CO fixation.

Herein, the exquisite combination of coplanar [Tm(CO)(μ-OH)(μ-HCO)(OH)] clusters ({Tm}) and structure-oriented functional BDCP leads to the highly robust nanoporous {Tm}-organic framework {(MeNH)[Tm(BDCP)(μ-OH)(μ-HCO)(HO)]·7DMF·5HO} (NUC-37, HBDCP = 2,6-bis(2,4-dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine). To the best of our knowledge, NUC-37 is the first anionic {Ln}-based three-dimensional framework with embedded hierarchical microporous and nanoporous channels, among which each larger one is shaped by six rows of coplanar {Tm} clusters and characterized by plentiful coexisting Lewis acid-base sites on the inner wall including open Tm sites, N atoms, μ-OH and μ-HCO. Catalytic experimental studies exhibit that NUC-37 possesses highly selective catalytic activity on the cycloaddition of epoxides with CO as well as high recyclability under gentle conditions, which should be ascribed to its nanoscale channels, rich bifunctional active sites, and stable physicochemical properties.

Nanochannel {InZn}-Organic Framework with a High Catalytic Performance on CO Chemical Fixation and Deacetalization-Knoevenagel Condensation.

The rare combination of In 5p and Zn 3d in the presence of a structure-oriented TDP ligand led to a robust hybrid material of {(MeNH)[InZn(TDP)(OH)]·4DMF·4HO} () with the interlaced hierarchical nanochannels (hexagonal and cylindrical) shaped by six rows of undocumented [InZn(CO)(OH)] clusters, which represented the first 5p-3d nanochannel-based heterometallic metal-organic framework. With respect to the multifarious symbiotic Lewis acid-base and Brønsted acid sites in the high porous framework, the catalytic performance of activated upon CO cycloaddition with styrene oxide was evaluated under solvent-free conditions with 1 atm of CO pressure, which exhibited that the reaction could be well completed at ambient temperature within 48 h or at 60 °C within 4 h with high yield and selectivity. Moreover, because of the acidic function of metal sites and a central free pyridine in the TDP ligand, deacetalization-Knoevenagel condensation of acetals and malononitrile could be efficiently facilitated by an activated sample of under lukewarm conditions.

Luminescent binuclear Zinc(II) organic framework as bifunctional water-stable chemosensor for efficient detection of antibiotics and Cr(VI) anions in water.

To achieve the ultrastable LMOFs with predominant luminescent sensing performances, the aromatic π-electron mixed ligands strategy was introduced, and the ternary LMOF of {[Zn(HDDB)(bib)]·3HO} (1), was fabricated based on 3,5-di(2',4'-dicarboxylphenyl)benozoic acid (HDDB) and the N-donor of meta-bis(imidazol-1-yl)benzene (bib) under mixed solvothermal condition. LMOF 1 features the first reported 3D 3,4,4-c {6.8.

Template-Induced {Mn}-Organic Framework with Lewis Acid-Base Canals as a Highly Efficient Heterogeneous Catalyst for Chemical Fixation of CO and Knoevenagel Condensation.

The target for the self-assembly of functional microporous metal-organic frameworks (MOFs) could be realized by employing ligand-directed and/or template-induced strategies, which prompted us to explore the synthetic technique of d secondary-building-unit-based nanoporous frameworks. Here, the exquisite combination of a paddle-wheel [Mn(CO)(OH)] cluster and a TDP ligand contributes one robust honeycomb framework of {(MeNH)[Mn(TDP)(HO)]·3HO·3DMF} (; DMF = ,-dimethylformamide), whose activated state with the removal of associated aqueous molecules characterizes the outstanding physicochemical properties of nanochannels, penta- and tetracoordinated Mn serving as highly open metal sites, rich Lewis base sites (rows of C═O groups and N atoms), and excellent thermal stability. Moreover, it is worth mentioning that Lewis acid-base sites on the inner surface of the channels in activated successfully form one unprecedented canal-shaped acid-base confined space with evenly distributed open metal sites of Mn and N atoms as the canal bottom as well as two rows of C═O groups serving as dyke dams.

V═O Functionalized {Tm}-Organic Framework Designed by Postsynthesis Modification for Catalytic Chemical Fixation of CO and Oxidation of Mustard Gas.

In terms of recently documented references, the introduction of V═O units into porous MOF/COF frameworks can greatly improve their original performance and expand their application prospects due to a change in their electronegativity. In this work, by a cation-exchange strategy, a consummate combination of separate 4f [Tm(CO)] SBUs and 3d [VO(HO)] units generated the functionalized porous metal-organic framework {(MeNH)[VO(HO)][Tm(BDCP)]·3DMF·3HO} (), in which [Tm(CO)] SBUs constitute the fundamental 3D host framework of {[Tm](BDCP)} along with [VO(HO)] units being further docked on the inner wall of channels by covalent bonds. Significantly, represents the first example of V═O modified porous MOFs, in which uncoordinated carboxylic groups (-COH) further grasp the functional [VO(HO)] units on the initial basic skeleton along with the formation of covalent bonds as fixed ropes.

6s-3d {BaZn}-Organic Framework as an Effective Heterogeneous Catalyst for Chemical Fixation of CO and Knoevenagel Condensation Reaction.

The exquisite combination of Ba and Zn with the aid of 2,4,6-tri(2,4-dicarboxyphenyl)pyridine (HTDP) under the condition of solvothermal self-assembly generates one highly robust [BaZn(CO)(HCO)(OH)]-organic framework of {[BaZn(TDP)(HCO)(OH)]·7DMF·4HO} (), in which adjacent 2D layers are interlaced via hydrogen-bonding interactions to form a 3D skeleton with peapod-like channels and nano-caged voids. It is worth emphasizing that both Ba and Zn ions in display the extremely low coordination modes: hexa-coordinated [Ba(1)] and tetra-coordinated [Ba(2), Zn(1), and Zn(2)]. Furthermore, to the best our knowledge, is one scarcely reported 2D-based nanomaterial with an unprecedented Z-shaped hepta-nuclear heterometallic cluster of [BaZn(CO)(HCO)(OH)] as SBUs, which not only has plentiful low-coordinated open metal sites but also has the excellent physicochemical properties including omni-directional opening pores, ultrahigh porosity, larger specific surface area, and the coexistence of Lewis acid-base sites.

Robust Heterometallic CoLa-Organic Framework for the Highly Efficient Separation of Acetylene from Light Hydrocarbon Mixtures.

A highly robust heterometallic CoLa-organic framework () is synthesized and features 1D rectangle-like channels with a window size of 3.4 × 6.3 Å and a carboxyl-group-modified inner surface.

One Robust Microporous Tm-Organic Framework for Highly Catalytic Activity on Chemical CO Fixation and Knoevenagel Condensation.

In terms of documented references, multifunctional MOFs with high catalytic performance could be constructed from the combination of metal cations and polycarboxyl-pyridine ligands, which could efficiently endow crystallized porous frameworks with the coexisting Lewis acid-base properties. Thus, by employing a ligand-directed synthetic strategy, the exquisite combination of wave-like inorganic chains of [Tm(CO)(OH)] and mononuclear units of [Tm(CO)(OH)] with the aid of the specially designed ligand of 2,6-bis(2,4-dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine (HBDCP) generates one highly robust microporous framework of {(MeNH)[Tm(BDCP))(HO)]·4DMF·HO} (simplified as ), which contains near-rectangular nanochannels and large solvent-residing voids. Furthermore, the activated state of with the removal of associated water molecules is a rarely reported bifunctional heterogeneous catalyst due to the coexistence of Lewis acid-base sites including 6-coordinated Tm ions, uncoordinated carboxyl oxygen atoms, and N atoms.

Highly Robust 3s-3d {CaZn}-Organic Framework for Excellent Catalytic Performance on Chemical Fixation of CO and Knoevenagel Condensation Reaction.

In terms of ligand-directed synthetic strategy, multifunctional metal-organic frameworks (MOFs) could be assembled by employing organic ligands with nitrogen-containing heterocycles, which could serve as Lewis base sites in crystallized porous frameworks. Here, the acidic one-pot hydrothermal reaction of CaCl, Zn(NO), and 2,4,6-tri(2,4-dicarboxyphenyl)pyridine (HTDP) generates one robust honeycomb-shaped double-walled material of {[(CH)NH][CaZn(TDP)(HO)]·3DMF·3HO} (), which has the excellent physicochemical characteristics of nanoscopic channels, high porosity (58.3%), large specific surface area, and high heat/water-resisting property.