Construction of Stable 2D Cationic Breathing Ni-MOF for Cr(VI) Trapping and Electrochemical Sensing.

Pollution of surface water by heavy metal hexavalent chromium ions poses a serious threat to human health; herein, a two-dimensional (2D) cationic breathing Ni-MOF with free nitrate ions between the layers was designed and synthesized according to the characteristics of hexavalent chromium ions, {[Ni(L)2](NO3)2·5H2O}n (L = 1,3,5-tris[4-(imidazol-1-yl)phenyl]benzene). The flexible layer spacing of the 2D breathing Ni-MOF allows the exchange of NO3- by CrO42- without destroying the original structure. Electrostatic and hydrogen bonding interactions between CrO42- and Ni-MOF facilitate its exchange with NO3-. Moreover, CrO42- exhibits a higher binding energy with Ni-MOF compared to NO3-, and the hydrophobic channels of Ni-MOF favor CrO42- trapping due to its lower hydration energy. Consequently, Ni-MOF demonstrates both effective sorption and electrochemical sensing of Cr(VI), achieving a sensitivity of 2.091 µA µM-1 and a detection limit of 0.07 µM.

Bottom-Up Construction of Rhombic Lamellar CoNi-MOFs for the Electrochemical Sensing of H2S.

Lamellar metal-organic frameworks (MOFs) have attracted significant attention in the field of electrochemical sensing due to their abundant open active sites and specific electron conductivity. Herein, by employing a bottom-up synthesis strategy, rhombic lamellar heterometallic CoNi-MOFs with varying thicknesses are constructed. This is achieved by using 4-methylpyridine as a capping agent based on the (4,6)-linked Co2(azpy)2(bptc) (azpy = 4,4'-azopyridine, bptc = 3,3',5,5'-biphenyltetracarboxylic acid) structure with a fsc topology and by introducing Ni species simultaneously. To mitigate sulfur deposition on electrodes, the triple pulse amperometry (TPA) method is employed. Among the synthesized lamellar CoNi-MOFs, lamellar CoNi-MOF-3 with the minimum thickness exhibits an optimal electrochemical sensing performance toward hydrogen sulfide, with a sensitivity of 119.3 µA·mM-1·cm-2 in the linear range of 2-2000 µM. This study pioneers a new approach to the controlled construction and electrochemical activity modification of lamellar MOF materials.

One Iron for Two Iron Sites in a Metal-Organic Framework Toward Simultaneous N2-H2 Activation under Mild Conditions.

Iron-based catalysts play an important role in the ammonia industry. As one of the most abundant iron minerals, Fe3O4 containing FeII and FeIII sites is widely distributed in the earth's crust and even on exoplanets, theoretically giving it both economic and catalytic potentials in ammonia synthesis. However, in the absence of specific active co-catalyst and harsh conditions, Fe3O4 is impossible to achieve ammonia synthesis alone. Here, we designed to activate the relatively inert FeII and FeIII sites in Fe3O4 with a third FeIII site inlayed in a coordination framework (MIL-101(Fe)) to achieve the unpresented multi-site collaborative catalysis. In-depth mechanism study confirmed the roles of three different Fe sites in N2 activation, H2 activation, and product transfer, respectively. Efficient N2-H2 activation to NH3 on the Fe3O4-based catalytic system has been achieved at extremely mild conditions. Our research provides a theoretical basis and a new strategy for designing efficient non-noble metal-based ammonia synthesis catalyst with minimized energy consumption.

Highly Robust Microporous Metal-Organic Frameworks for Efficient Ethylene Purification under Dry and Humid Conditions.

Two C2 H6 -selective metal-organic framework (MOF) adsorbents with ultrahigh stability, high surface areas, and suitable pore size have been designed and synthesized for one-step separation of ethane/ethylene (C2 H6 /C2 H4 ) under humid conditions to produce polymer-grade pure C2 H4 . Experimental results reveal that these two MOFs not only adsorb a high amount of C2 H6 but also display good C2 H6 /C2 H4 selectivity verified by fixed bed column breakthrough experiments. Most importantly, the good water stability and hydrophobic pore environments make these two MOFs capable of efficiently separating C2 H6 /C2 H4 under humid conditions, exhibiting the benchmark performance among all reported adsorbents for separation of C2 H6 /C2 H4 under humid conditions. Moreover, the affinity sites and their static adsorption energies were successfully revealed by single crystal data and computation studies. Adsorbents described in this work can be used to address major chemical industrial challenges.

Surface Modification of Nano-Cu2 O for Controlling CO2 Electrochemical Reduction to Ethylene and Syngas.

In the surroundings of carbon neutrality, nano-Cu2 O is considered a promising catalyst for the electrochemical CO2 reduction reaction (ECO2 RR), whose improvements in product selectivity still require considerable efforts. Here, we present an efficient strategy for controlling the ECO2 RR product by modifying the surface of nano-Cu2 O, i.e., by controlling the exposed facets via a reductant-controlled method to achieve the highest C2 H4 selectivity (Faradic efficiency=74.1 %) for Cu2 O-based catalysts in neutral electrolytes, and introducing a well-suited metal-organic framework (MOF) coating on the surface of nano-Cu2 O to obtain syngas completely with an appropriate H2 :CO ratio. Detailed mechanism and key intermediate have been illustrated by DFT calculations. Our systematic strategy is expected to control the ECO2 RR product, improve the selectivity, and provide a reliable method for CO2 management and the green production of important carbon resources.

Fabrication of Moisture-Responsive Crystalline Smart Materials for Water Harvesting and Electricity Transduction.

It is of profound significance with regard to the global energy crisis to develop new techniques and materials that can convert the chemical potential of water into other forms of energy, especially electricity. To address this challenge, we built a new type of energy transduction pathway (humidity gradients → mechanical work → electrical power) using moisture-responsive crystalline materials as the media for energy transduction. Single-crystal data revealed that a flexible zeolitic pyrimidine framework material, ZPF-2-Co, could undergo a reversible structural transformation (ß to α phase) with a large unit cell change upon moisture stimulus. Dynamic water vapor sorption analysis showed a gate-opening effect with a steep uptake at as low as 10% relative humidity (RH). The scalable green synthesis approach and the fast water vapor adsorption-desorption kinetics made ZPF-2-Co an excellent sorbent to harvest water from arid air, as verified by real water-harvesting experiments. Furthermore, we created a gradient distribution strategy to fabricate polymer-hybridized mechanical actuators based on ZPF-2-Co that could perform reversible bending deformation upon a variation of the humidity gradient. This mechanical actuator showed remarkable durability and reusability. Finally, coupling the moisture-responsive actuator with a piezoelectric transducer further converted the mechanical work into electrical power. This work offers a new type of moisture-responsive smart material for energy transduction and provides an in-depth understanding of the responsive mechanism at the molecular level.

Controlled Thermal Conversion Strategy to Provide Metal-Organic Framework-Supported Composite Catalysts.

Metal-organic framework (MOF)-supported metal/metal compound nanoparticles (NPs) have emerged as a new class of composite catalysts. However, huge challenges prevail in placing such NPs in the MOF pores because of the poor solubility of metal/metal oxides, limited availability of suitable precursors, metastable attribute of given metal ions, and lower thermal stability of MOFs compared to conventional porous materials. Based on the difference between the thermal stability of the precursor and MOFs, we successfully developed a controlled thermal conversion (CTC) method to load cobalt(II) oxide (CoO) NPs into the framework of MOF (MIL-101) to conveniently obtain a composite catalyst, CoO@MIL-101, which is a very rare example of pure CoO NP-loaded composite catalyst that shows excellent catalytic activity in the selective oxidation of benzyl alcohol. This CTC strategy opens up a pathway for impregnating MOF supports with specific NPs, which is further confirmed by preparing the first CuBr@MOF-type composite catalyst.

Construction of CuII Defects on CuCl Nanoparticles in Metal-Organic Frameworks toward Composite Catalysts with Superior Activity.

Metal-organic frameworks (MOFs) represent an ideal platform for the construction of highly active composite catalysts. However, loading metastable and/or multicomponent metal compounds into MOFs remains a synthetic bottleneck due to the great challenge of keeping the guest and matrix intact during the preparation of a composite. In this work, we develop a new impregnation reduction surface modification (IRSM) strategy to give a new composite catalyst CuCl@MIL-101(Cr), which is successfully postmodified by in situ construction of CuII defects on the surface of loaded CuCl inside MOF pores, leading to the new composite material CuII/CuI@MIL-101(Cr). The new dual-component composite catalyst exhibits a hierarchical structure and superior catalytic activity in C-C homocoupling of arylboronic acids under green conditions. This study presents a facile strategy for improving the catalytic activity by constructing defects on the surface of MOF-based catalysts as well as for forming multiple-component composite materials.

Integration of Metal Nanoparticles into Metal-Organic Frameworks for Composite Catalysts: Design and Synthetic Strategy.

Metal-organic frameworks (MOFs) are constructed by periodically alternate metal ions with organic ligands, which offer structural diversity and a wide range of interesting properties as an attractive classification of crystalline porous materials. Integration of MOFs with other size-limited functional centers can supply new multifunctional composites, which exhibit both the properties of the components and new characteristics due to the combination of MOFs with the selected loadings. In recent years, integration of metal/metal oxide nanoparticles (MNPs) into MOFs to form the composite catalysts has attracted considerable attention due to the superior performance. In this review, the latest studies and up-to-date developments on the design and synthetic strategy of new MNP@MOF composite catalysts are specifically highlighted. Both the achievements and problems are evaluated and proposed, and the opportunities and challenges of MNP@MOF composite catalysts are discussed.

Pressure Sensor with a Color Change at Room Temperature Based on Spin-Crossover Behavior.

Two new iron(II) complexes with 1D chain and 2D network structures have been successfully synthesized and characterized. One of the complexes exhibits a pressure-induced spin-crossover property with a reversible color change from white to purple at room temperature. The special property makes it a suitable candidate as a pressure sensor.

Silica-Protection-Assisted Encapsulation of Cu2 O Nanocubes into a Metal-Organic Framework (ZIF-8) To Provide a Composite Catalyst.

The integration of metal/metal oxide nanoparticles (NPs) into metal-organic frameworks (MOFs) to form composite materials has attracted great interest due to the broad range of applications. However, to date, it has not been possible to encapsulate metastable NPs with high catalytic activity into MOFs, due to their instability during the preparation process. For the first time, we have successfully developed a template protection-sacrifice (TPS) method to encapsulate metastable NPs such as Cu2 O into MOFs. SiO2 was used as both a protective shell for Cu2 O nanocubes and a sacrificial template for forming a yolk-shell structure. The obtained Cu2 O@ZIF-8 composite exhibits excellent cycle stability in the catalytic hydrogenation of 4-nitrophenol with high activity. This is the first report of a Cu2 O@MOF-type composite material. The TPS method provides an efficient strategy for encapsulating unstable active metal/metal oxide NPs into MOFs or maybe other porous materials.

Composite System of Ag Nanoparticles and Metal-Organic Frameworks for the Capture and Conversion of Carbon Dioxide under Mild Conditions.

The materials Ag@MIL-100(Fe) and Ag@UIO-66(Zr) are obtained for the capture and transformation of CO2 into alkynyl carboxylic acids, which are environmental friendly, facile to synthesize, and exhibit excellent efficiency and reusability. The influence on the catalytic activity of such Ag@MOF systems by metal-organic frameworks' (MOFs) surface area, thermal, and chemical stability, especially the acid-base characteristics of the pores, are compared and discussed systematically.

Coordination-Driven Polymerization of Supramolecular Nanocages.

Controlled assembly of 0D supramolecular nanocages into 2D or 3D architectures has been demonstrated for the first time via a coordination-driven polymerization approach, and the conversion from a 2D to 3D supramolecular architecture has also been successfully achieved via a temperature-induced crystal transformation. The boost of dimensionality for the supramolecular architecture has led to steady yet remarkable enhancement of properties, as reflected from the gas adsorption studies.

An efficient nanoscale heterogeneous catalyst for the capture and conversion of carbon dioxide at ambient pressure.

Silver nanoparticles were successfully supported on the zeolite-type metal-organic framework MIL-101 to yield Ag@MIL-101 by a simple liquid impregnation method. For the first time, the conversion of terminal alkynes into propiolic acids with CO2 was achieved by the use of the Ag@MIL-101 catalysts. Owing to the excellent catalytic activity, the reaction proceeded at atmospheric pressure and low temperature (50 °C). The Ag@MIL-101 porous material is of outstanding bifunctional character as it is capable of simultaneously capturing and converting CO2 with low energy consumption and can be recovered easily by centrifugation.

Molecular enhancement of Cu-based catalysts for CO2 electroreduction.

The electrochemical carbon dioxide reduction reaction (eCO2RR) represents an effective means of achieving renewable energy storage and a supply of carbon-based raw materials. However, there are still great challenges in selectively producing specific hydrocarbon compounds. The unique ability of the copper (Cu) catalyst to promote proton-coupled electron transfer processes offers clear advantages in generating value-added products. This review presents molecular enhancement strategies for Cu-based catalysts for CO2 electroreduction. We also elucidate the principles of each strategy for enhancing eCO2RR performance, discuss the structure-activity relationships, and propose some promising molecular enhancement strategies. This review will provide guidance for the development of organic-inorganic hybrid Cu-based catalysts as high-performance CO2 electroreduction catalysts.

3-O-Methyl-D-Glucose Blunts Cold Ischemia Damage in Kidney via Inhibiting Ferroptosis.

BACKGROUND: The glucose derivative 3-O-methyl-D-glucose (OMG) is used as a cryoprotectant in freezing cells. However, its protective role and the related mechanism in static cold storage (CS) of organs are unknown. The present study aimed to investigate the effect of OMG on cod ischemia damage in cold preservation of donor kidney. METHODS: Pretreatment of OMG on kidney was performed in an isolated renal cold storage model in rats. LDH activity in renal efflux was used to evaluate the cellular damage. Indicators including iron levels, mitochondrial damage, MDA level, and cellular apoptosis were measured. Kidney quality was assessed via a kidney transplantation (KTx) model in rats. The grafted animals were followed up for 7 days. Ischemia reperfusion (I/R) injury and inflammatory response were assessed by biochemical and histological analyses. RESULTS: OMG pretreatment alleviated prolonged CS-induced renal damage as evidenced by reduced LDH activities and tubular apoptosis. Kidney with pCS has significantly increased iron, MDA, and TUNEL+ cells, implying the increased ferroptosis, which has been partly inhibited by OMG. OMG pretreatment has improved the renal function (p <0.05) and prolonged the 7-day survival of the grafting recipients after KTx, as compared to the control group. OMG has significantly decreased inflammation and tubular damage after KTx, as evidenced by CD3-positive cells and TUNEL-positive cells. CONCLUSION: Our study demonstrated that OMG protected kidney against the prolonged cold ischemia-caused injuries through inhibiting ferroptosis. Our results suggested that OMG might have potential clinical application in cold preservation of donor kidney.

Hierarchical surface-modification of nano-Cu toward one pot H-transfer-coupling-cyclization-CO2 fixation tandem reactions.

Fixation of CO2 into dihydroisobenzofuran derivatives has enormous applications in both production of natural products and antidepressant drugs, and reducing the green-house effect. However, the relatively complicated multi-step processes limit the further expansion of such a valuable CO2 conversion strategy. Herein, we hierarchically modify the surface of Cu nanoparticles (NPs) with Ag NPs and the robust metal-organic framework (MOF), ZIF-8, and report the presence of the Cu-Ag yolk-shell nanoalloy based heterogeneous catalysts, Cu@Ag and Cu@Ag@ZIF-8. The latter exhibits a crystalline "raisin bread" structure and specific synergic activity for catalyzing the tandem reactions of intra-molecular H-transfer, C-C and C-O coupling, cyclization, and carboxylation from CO2, leading to the first non-homogeneous preparation of dihydroisobenzofuran derivatives in high yield, selectivity, and recyclability under mild conditions. Theoretical calculations elucidate the tandem reaction pathway synergically catalyzed by Cu@Ag@ZIF-8, which offers insights for designing multiphase catalysts towards both organic synthesis and CO2 fixation through tandem processes in one pot.

Synthesis and chirality control of bulk crystals and nanocrystals: from a right-handed nonpolar chain to a left-handed polar chain.

Both bulk crystals and nanocrystals of two helical complexes, [Cu(µ2-L)(H2O)]n (1) and {[Cu(µ2-L)(H2O)]·2H2O}n (2) (H2L = thiazolidine-2,4-dicarboxylic acid), have been synthesized with the chiralities of right-handedness (1) and left-handedness (2), respectively. 4-Cyanopyridine and poly(vinylpyrrolidone) (PVP) have been applied to control the synthesis of complexes with different helicities in bulk-crystal and nanocrystal forms, respectively. 2 can be irreversibly transformed to 1 under heating. Associated with the conformation changing, the symmetry alters between nonpolar and polar space groups.

Tailored Sky-Parking Architectures of 3D Graphene Oxide Towards Highly-Efficient Water Purification.

The widespread use of chemicals has brought serious water pollution threatening human health and environment, which requires green, fast, and low-cost purification urgently. Here, we build up a novel material family of sky-parking-like 3D structured graphene oxides (SP-GOs) with adjustable interlayer-space of 0.8-1.7 nm via the insertion of different sized diamine compounds as support pillars between GO layers. The assembled 3D SP-GOs exhibit superior adsorption capacity and short removal time for various aromatic organic compounds in water, achieving record-breaking maximum adsorption capacity of 535.79 mg g-1 toward the most common water-pollutant bisphenol A (BPA) at ambient conditions as well as significantly improved removal of other organic pollutants including sulfapyridine, carbamazepine, ketoprofen and 2-naphthol. The construction of SP-GO provides a simple approach for evolving the GO material from 2D to 3D and a new avenue for the decontamination of pollutants in environmental remediation.

Ultrastable Cu-Based Dual-Channel Heterowire for the Switchable Electro-/Photocatalytic Reduction of CO2.

Catalytic conversion of CO2 into high value-added chemicals using renewable energy is an attractive strategy for the management of CO2 . However, achieving both efficiency and product selectivity remains a great challenge. Herein, a brand-new family of 1D dual-channel heterowires, Cu NWs@MOFs are constructed by coating metal-organic frameworks (MOFs) on Cu nanowires (Cu NWs) for electro-/photocatalytic CO2 reductions, where Cu NWs act as an electron channel to directionally transmit electrons, and the MOF cover acts as a molecule/photon channel to control the products and/or undertake photoelectric conversion. Through changing the type of MOF cover, the 1D heterowire is switched between electrocatalyst and photocatalyst for the reduction of CO2 with excellent selectivity, adjustable products, and the highest stability among the Cu-based CO2 RR catalysts, which leads to heterometallic MOF covered 1D composite, and especially the first 1D/1D-type Mott-Schottky heterojunction. Considering the diversity of MOF materials, the ultrastable heterowires offer a highly promising and feasible solution for CO2 reduction.