3D Metal-organic Framework Research Articles

Synthesis of 2D bi-metallic Zn/Cu metal-organic framework integrated graphene nanocomposites for all-solid-state asymmetric supercapacitors

In this work, a novel two-dimensional (2D) bi-metallic metal-organic frameworks (MOFs) consisting of zinc and copper metal centers with 1,3,5-tricarboxylic acid as a chief and efficient organic linker (Zn/Cu-BTC) and its composite with exfoliated graphene nanosheets (EGNSs) have been investigated for supercapacitor applications. The composites were synthesized via facile in-situ solvothermal process. Different spectroscopic, microscopic, and surface analyses confirmed the successful formation of porous electroactive composites, where 2D MOF nanosheets were vertically grown on the EGNS surfaces. In the two-electrode symmetric system, the as-synthesized Zn/Cu-BTC MOF@EGNS electrode achieved an enhanced specific gravimetric capacitance and equivalent volumetric capacitance of 1284.9 F/g and 813.3 F/cm3 at 0.5 A/g. It exhibits high-rate performance and prolonged cycling stability with >90 % retention after 8000 cycles. All-solid-state asymmetric supercapacitor (ASC) device was constructed with Zn/Cu-BTC MOF@EGNS composite and EGNS electrodes, where PVA-KOH membrane served as a separator-cum-electrolyte. The ASC device delivered a satisfactory energy density of 60.55 Wh kg−1 and a maximum power density of 10 kW kg−1 with an admirable cycling stability of 92 % after 10,000 charge-discharge cycles. In the future, this work can encourage manufacturing innovation.

Electrodeposition of gold-platinum nanoparticles on 2D M-TCPP (M = Co, Cu, Zn) for electrochemical monitoring of H2O2 from living cells

Two-dimensional (2D) metal–organic frameworks (MOFs) as supporting nanomaterials to encapsulate or load metal nanoparticles have been widely applied in electrochemical sensing. Therefore, the influences of tetrakis(4-carboxyphenyl) porphyrin-based MOFs (M-TCPP (M = Co, Cu, Zn)) as supporting materials on the electrocatalytic activity were studied. A surfactant-assisted method was employed to facilely synthesize three types of 2D M-TCPP nanosheet MOFs. Polyvinylpyrrolidone was selected as a surfactant for preparing M-TCPP and played a key role in the controlled anisotropic growth of MOF crystals, resulting in the formation of 2D MOF nanosheets. Then, one-step electrodeposition of gold-platinum nanoparticles (AuPt NPs) on the M-TCPP-modified glassy carbon electrode (AuPt/M-TCPP/GCE) was explored for reducing hydrogen peroxide (H2O2). Cyclic voltammetry was applied to investigate the electrocatalytic performance of AuPt/M-TCPP/GCE, and AuPt/Cu-TCPP/GCE exhibited better electrocatalytic characteristics than AuPt/Co-TCPP/GCE and AuPt/Zn-TCPP/GCE. The electrochemical H2O2 sensor displayed a low detection limit of 3.1 nM in the wide concentration range of 0.01 μM to 80 mM. In addition, the proposed sensor showed high stability, good reproducibility, and selectivity. Moreover, HepG2 human liver cancer cells were selected for real-time detection of H2O2 to verify the feasibility of this technology for the evaluation of anticancer drugs. The results showed that Cu-TCPP can be used as an efficient supporting material for enhancing the detection property of electrochemical sensors.

Hydrothermal Assembly, Structural Multiplicity, and Catalytic Knoevenagel Condensation Reaction of a Series of Coordination Polymers Based on a Pyridine-Tricarboxylic Acid.

A pyridine-tricarboxylic acid, 5-(3',5'-dicarboxylphenyl)nicotinic acid (H3dpna), was employed as a adjustable block to assemble a series of coordination polymers under hydrothermal conditions. The seven new coordination polymers were formulated as [Co(μ3-Hdpna)(μ-dpey)]n·nH2O (1), [Zn4.5(μ6-dpna)3(phen)3]n (2), [Co1.5(μ6-dpna)(2,2'-bipy)]n (3), [Zn1.5(μ6-dpna)(2,2'-bipy)]n (4), [Co3(μ3-dpna)2(4,4'-bipy)2(H2O)8]n·2nH2O (5),[Co(bpb)2(H2O)4]n[Co2(μ3-dpna)2(H2O)4]n·3nH2O (6), and [Mn1.5(μ6-dpna)(μ-dpea)]n (7), wherein 1,2-di(4-pyridyl)ethylene (dpey), 1,10-phenanthroline (phen), 2,2'-bipyridine(2,2'-bipy),4,4'-bipyridine(4,4'-bipy),1,4-bis(pyrid-4-yl)benzene (bpb), and 1,2-di(4-pyridyl)ethane (dpea) were employed as auxiliary ligands. The structural variation of polymers 1-7 spans the range from a 2D sheet (1-4, 6, and 7) to a 3D metal-organic framework (MOF, 5). Polymers 1-7 were investigated as heterogeneous catalysts in the Knoevenagel condensation reaction, leading to high condensation product yields (up to 100%) under optimized conditions. Various reaction conditions, substrate scope, and catalyst recycling were also researched. This work broadens the application of H3dpna as a versatile tricarboxylate block for the fabrication of functional coordination polymers.

Identifying topological corner states in two-dimensional metal-organic frameworks

Due to the diversity of molecular building blocks, the two-dimensional (2D) metal-organic frameworks (MOFs) are ideal platforms to realize exotic lattice models in condensed matter theory. In this work, we demonstrate the universal existence of topological corner states in 2D MOFs with a star lattice configuration, and confirm the intriguing higher-order nontrivial topology in the energy window between two Kagome-bands, or between Dirac-band and four-band. Furthermore, combining first-principles calculations and scanning tunneling microscopy measurements, the unique topological corner state is directly identified in monolayer Ni3(HITP)2 (HITP = 2,3,6,7,10,11-hexaiminotriphenylene) grown on the Au(111) substrate. Our results not only illustrate the first organic topological state in the experiments, but also offer an exciting opportunity to study higher-order topology in 2D MOFs with the large insulating band gap.

MOF-derived 2D Co@C nanosheet membrane with enhanced catalytic activity: Mechanism and stability insights

Two-dimensional (2D) metal-organic frameworks (MOFs) membranes have recently gained attention as novel material membranes for advanced oxidation processes (AOPs). Nonetheless, the susceptibility of 2D MOFs to reactive oxygen species (ROS) limits 2D MOF membranes’ effectiveness in AOPs. In this study, we introduce a novel approach, fabricating a 2D Co-MOF-derived nanosheet membrane (referred to as Co@C NS), assembled from pyrolyzed and exfoliated Co-MOF nanosheets, for the activation of peroxymonosulfate (PMS) in the removal of bisphenol A (BPA). Crucially, the synthesis process involves the pyrolysis of a carbon layer, serving as a protective barrier. This barrier effectively prevents the release of Co ions, ensuring the long-term structural and catalytic stability of the Co@C NS membrane. Notably, the membrane exhibits remarkable capabilities in discriminating between natural organic matter (NOM) and BPA through size exclusion, significantly mitigating the impact of NOM competition for ROS. Additionally, our study demonstrates an exceptional removal efficiency, achieving 100% BPA removal at an ultrahigh permeance of 1100 L m−2 h−1 bar−1, corresponding to an exceedingly short retention time of 0.14 s. Our mechanistic investigation reveals the involvement of singlet oxygen and sulfate radicals in the removal of BPA within the nanochannels, facilitated by the nanoconfinement effect. This study introduces valuable strategies for the development of 2D MOF-derived nanosheet membranes characterized by high catalytic activity and excellent stability, underlining their practical potential in AOP applications.

Two-Dimensional Cu-Porphyrin Metal-Organic Framework Nanosheet-Supported Flaky TiO2 as an Efficient Visible-Light-Driven Photocatalyst for Dye Degradation and Cr(VI) Reduction.

A series of 2D M(Cu, Zn, Co, and Mn)-TCPP MOFs/TiO2 binary nanocomposites (TCPP = tetrakis(4-carboxyphenyl)porphyrin) were constructed by solvothermal in situ loading of flaky TiO2 on the surface of 2D metal-organic frameworks (MOFs). The influence of different coordination metals on the catalytic activity was studied, and it was found that the 2D Cu-TCPP MOFs/TiO2 nanocomposite exhibited the best photo-Fenton performance. The superior property can be attributed to the high absorption coefficient and ultrathin two-dimensional structure of the 2D Cu-TCPP MOFs nanosheets. Meanwhile, the 2D Cu-TCPP MOFs/TiO2 II heterostructure can effectively promote the separation and transfer of photoformed carriers. Moreover, under visible irradiation, the optimized 2D Cu-TCPP MOFs/TiO2 composite can convert 99.9% of Cr(VI) to Cr(III) within 60 min with methanol as the hole scavenger at pH 3.14. Also, the photocatalytic performance of 2D Cu-TCPP MOFs/TiO2 was maintained after five reaction cycles. Furthermore, the proposed visible-light-driven photocatalysis mechanism of the 2D Cu-MOFs/TiO2 composite was reasonably derived according to experimental results. This study demonstrates the potential of building efficient TiO2-based visible light photocatalysts with 2D metal-porphyrin MOFs.

Viologen Guest-Mediated Luminescence Emission Tuning and Photochromic Behavior by a Series of Viologen@Zn-MOF Materials.

The encapsulation of various guest molecules into the pores of metal-organic frameworks (MOFs) to form hybrid materials has attracted significant attention due to their unique spatial distribution and certain preferential geometry of the guests inside the MOFs. This arrangement often results in the guests exhibiting unique physical and chemical properties due to their intramolecular interactions with the host. In this article, five viologen derivatives were introduced as guests in a Zn-MOF with different benzene ring lengths, resulting in the formation of host-guest three-dimensional (3D) MOFs. The five compounds exhibited guest-dependent emission wavelength, color, and excellent photochromic behavior upon ultraviolet (UV) light radiation due to the distinct electronic transfer and π···π stacking interactions between the viologen guests and the host framework. This study provides a host-guest strategy for designing color-tunable luminescent and highly sensitive photochromic materials.

Coordination Polymers from an Amino-Functionalized Terphenyl-Tetracarboxylate Linker: Structural Multiplicity and Catalytic Properties.

An amino-functionalized terphenyl-tetracarboxylic acid, 2'-amino-[1,1':4',1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid (H4tpta), was used as an adaptable linker to synthesize, under hydrothermal conditions, eight coordination polymers (CPs). The obtained products were formulated as [Co(μ6-H2tpta)]n (1), [Co(μ3-H2tpta)(2,2'-bipy)]n (2), [M3(μ6-Htpta)2(2,2'-bipy)2]n (M = Mn (3), Cd (4)), [Ni2(μ4-tpta)(phen)2(H2O)4]n (5), [Zn2(μ6-tpta)(phen)2]n (6), {[Zn2(μ6-tpta)(μ-4,4'-bipy)]·H2O}n (7), and [Zn2(μ6-tpta)(μ-H2biim)(H2O)2]n (8), wherein 2,2'-bipyridine (2,2'-bipy), 4,4'-bipyridine (4,4'-bipy), 1,10-phenanthroline (phen), or 2,2'-biimidazole (H2biim) are present as additional stabilizing ligands. The structural types of 1-8 vary from one-dimensional (1D) (2, 5) and two-dimensional (2D) (3, 4, 6) CPs to three-dimensional (3D) metal-organic frameworks (MOFs) (1, 7, and 8) with a diversity of topologies. The products 1-8 were investigated as catalysts in the Knoevenagel condensation involving aldehydes and active methylene derivatives (malononitrile, ethyl cyanoacetate, or tert-butyl cyanoacetate), leading to high condensation product yields (up to 99%) under optimized conditions. Various reaction conditions, substrate scope, and catalyst recycling were investigated. This work broadens the application of H4tpta as a versatile tetracarboxylate linker for the generation of diverse CPs/MOFs.

Ag Nanoparticles-Induced Metallic Conductivity in Thin Films of 2D Metal-Organic Framework Cu3(HHTP)2.

Two-dimensional (2D) metal-organic frameworks (MOFs) are usually associated with higher electrical conductivity and charge carrier mobility when compared with 3D MOFs. However, attaining metallic conduction in such systems through synthetic or postsynthetic modifications is extremely challenging. Herein, we present the fabrication of thin films of a 2D MOF, Cu3(HHTP)2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene), decorated with silver nanoparticles (AgNPs) exhibiting significant conductivity enhancement at room temperature. Variable-temperature electrical transport measurements across the low-temperature (200 K) to high-temperature (373 K) regime evidenced metallic conduction. Interestingly, thin films of a 3D MOF, CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane), upon decoration with AgNPs, disclosed a converse trend. The origin of such distinctive observations on AgNPs@Cu3(HHTP)2 and AgNPs@CuTCNQ systems was comprehended by using first-principles density functional theory (DFT) calculations and attributed to an interfacial electronic effect. Our work sheds new light on rationally designing synthetic modifications in thin films of MOFs to tune the electrical transport property.

A Triptycene-Based Layered/Flower-Like 2D Conductive Metal-Organic Framework with 3D Extension as an Electrode for Efficient Li Storage.

2D metal-organic frameworks (2D MOFs) with π conjugation have attracted widespread attention in the field of lithium storage due to their unique electron transfer units and structural characteristics. However, the periodic 2D planar extension structure hides some active sites, which is not conducive to the utilization of its structural advantages. In this work, a series of triptycene-based 2D conductive MOFs (M-DBH, M = Ni, Mn, and Co) with 3D extension structures are constructed by coordinating 9,10-dihydro-9,10-[1,2]benzenoanthracene-2,3,6,7,14,15-hexaol with metal ions to explore their potential applications in lithium-ion and lithium-sulfur batteries. This is the first study in which 2D conductive MOFs with the 3D extended molecule are used as electrode materials for lithium storage. The designed material generates rich active sites through staggered stacking layers and shows excellent performance in lithium-ion and lithium-sulfur batteries. The capacity retention rate of Ni-DBH can reach over 70% after 500 cycles at 0.2 C in lithium-ion batteries, while the capacity of S@Mn-DBH exceeds 305 mAhg-1 after 480 cycles at 0.5 C in lithium-sulfur batteries. Compared with the materials with 2D planar extended structures, the M-DBH electrodes with 3D extended structures in this work exhibit better performance in terms of cycle time and lithium storage capacity.

Synthesis of Two-Dimensional (Cu-S)n Metal-Organic Framework Nanosheets Applied as Peroxidase Mimics for Detection of Glutathione.

Facilely synthesized peroxidase-like nanozymes with high catalytic activity and stability may serve as effective biocatalysts. The present study synthesizes peroxidase-like nanozymes with multinuclear active sites using two-dimensional (2D) metal-organic framework (MOF) nanosheets and evaluates them for their practical applications. A simple method involving a one-pot bottom-up reflux reaction is developed for the mass synthesis of (Cu-S)n MOF 2D nanosheets, significantly increasing production quantity and reducing reaction time compared to traditional autoclave methods. The (Cu-S)n MOF 2D nanosheets with the unique coordination of Cu(I) stabilized in Cu-based MOFs demonstrate impressive activity in mimicking natural peroxidase. The active sites of the peroxidase-like activity of (Cu-S)n MOF 2D nanosheets were predominantly verified as Cu(I) rather than Cu(II) of other Cu-based MOFs. The cost-effective and long-term stability of (Cu-S)n MOF 2D nanosheets make them suitable for practical applications. Furthermore, the inhibition of the peroxidase-like activity of (Cu-S)n MOF nanosheets by glutathione (GSH) could provide a simple strategy for colorimetric detection of GSH against other amino acids. This work remarkably extends the utilization of (Cu-S)n MOF 2D nanosheets in biosensing, revealing the potential for 2D (Cu-S)n MOFs.

Self-assembled superhydrophilic MOF-decorated membrane for highly efficient treatment and separation mechanism of multi-component emulsions

Complex multi-component pollutant-oil-water emulsions have caused serious environmental problems and increased the difficulty of purification treatment in the last few decades. The membrane based on two-dimensional (2D) materials can rationally control the interlayer distance, thus improved the separation performance of the membrane for complex wastewater. We herein reported a composite membrane, in which 2D metal-organic frameworks (MOFs) Co-CAT-1 with super-hydrophilicity cross-linked by polyethylene imine (PEI) was integrated into graphene oxide (GO) and then coated on polyvinylidene fluoride (PVDF) membrane (CPG membrane). The CPG membrane exhibited highly efficient in separating oil-water (including crude oil) emulsions, achieving a flux of 219 L∙m−2∙h−1∙bar−1 and a separation efficiency of 99.2 %. Moreover, the separation efficiency for complex emulsions after several cycles was maintained >99 % for dyes and 76 % for heavy metal ions (Ni2+, Pb2+, Zn2+). The remarkable fouling resistance and reusability of CPG membrane in purifying complex oil-in-water emulsions can be attributed to their internal cross-linking, electrostatic interactions, hydrogen bonding attraction, and π-π stacking. Molecular dynamics simulations were employed for in-depth studies on the separation processes of dye- and heavy metal ions-emulsions, revealing the mechanisms of mass transfer within the membrane. This work aims to construct stable and multifunctional membranes for separating pollutant-oil-water emulsions with multi-component.

Incorporating a D-A-D-Type Benzothiadiazole Photosensitizer into MOFs for Photocatalytic Oxidation of Phenylsulfides and Benzylamines.

Oxidation and removal of highly toxic sulfides and amines are particularly important for environmental and human security but remain challenging. Here, incorporating an excellent photosensitizer, donor-acceptor-donor (D-A-D)-type 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoic (H2L), into metal-organic frameworks (MOFs) has been manifested to promote the charge separation, affording four three-dimensional (3D) MOFs (isostructural 1-Co/1-Zn with Co2/Zn2 units, and 2-Gd/2-Tb with Gd/Tb-cluster chains) as photocatalysts in the visible light-driven air-O2-mediated catalytic oxidation and removal of hazardous phenylsulfides and benzylamines. Impressively, structure-property correlation illustrated that the transition metal centers assembled in MOFs play an important role in the photocatalytic activity, and we can conclude that 1-Zn can be a robust heterogeneous catalyst possessing good light adsorption and fast charge separation in oxidation removal reactions of both benzylamines and phenylsulfides under visible light irradiation and room temperature with excellent activity/selectivity, stability, and reusability.

Theoretical Prediction of Electrocatalytic Reduction of CO2 Using a 2D Catalyst Composed of 3 d Transition Metal and Hexaamine Dipyrazino Quinoxaline.

Transition metals and organic ligands combine to form metal-organic frameworks (MOFs), which possess distinct active sites, large specific surface areas and stable porous structures, giving them considerable promise for CO2 reduction electrocatalysis. In the present study, using spin polarisation density-functional theory, a series of 2D MOFs constructed from 3d transition metal and hexamethylene dipyrazoline quinoxaline(HADQ) were investigated. The calculated binding energies between HADQ and metal atoms for the ten TM-HADQ monolayers were strong sufficient to stably disperse the metal atoms in the HADQ monolayers. Of the ten catalysts tested, seven (Sc, Ni, Cu, Zn, Ti, V and Cr) exhibited high CO2 reduction selectivity, while Mn, Fe and Co required pH values above 2.350, 6.461 and 6.363, respectively, to exhibit CO2 reduction selectivity. HCOOH was the most important producer for Sc, Zn, Ni and Mn, while CH4 was the main producer for Ti, Cr, Fe and V. Cu and Co were less selective, producing HCHO, CH3 OH, and CH4 simultaneously at the same rate-determining step and limiting potential. The Cu-HADQ catalyst had a high overpotential for the HCHO product (1.022 V), while the other catalysts had lower overpotentials between 0.016 V and 0.792 V. Thus, these results predict TM-HADQ to show excellent activity in CO2 electrocatalytic reduction and to become a promising electrocatalyst for CO2 reduction.

Thin film nanocomposite membranes fabricated via 2D ZIF-67 nanosheets and 1D nanofibers with ultrahigh water flux for dye removal from wastewater

Thin-film nanocomposite (TFN) membranes based on metal–organic frameworks (MOFs) have received increasing attention in the field of water treatment. However, TFN membranes with both high permeance and rejection rates are highly desired. In this study, ultra-thin ZIF-67 was synthesized and TFN membranes were fabricated by combining the obtained 2D ZIF-67 with cellulose nanofibers (CNF) and carbon nanotubes (CNTs). The nanofibers not only fill the gaps between the ZIF-67 nanosheets but also form an intercalation layer between the ZIF-67 nanosheets and function as a water transport pathway, leading to a significant enhancement of water permeance. By introducing CNF into the ZIF-67-embedded matrix, the dye rejection rates increase to 96.8 % and 93.3 %, respectively, with water permeance of about 90.0 L⋅m−2⋅h−1⋅bar−1. Further introducing CNT into the CNF/ZIF-67 membrane further improved the water permeance to 207.8 L⋅m−2⋅h−1⋅bar−1, while a dye rejection rate of 95.1 % was documented. The results indicate that the introduction of nanofibers into 2D MOF matrix to form TFN membranes has great potential for wastewater treatment.

Decorating Channel Walls in Metal–Organic Frameworks with Crown Ethers for Efficient and Selective Separation of Radioactive Strontium(II)

AbstractNuclear accidents and the improper disposal of nuclear wastes have led to serious environmental radioactive pollutions. The rational design of adsorbents for the highly efficient separation of strontium(II) is essential in treating nuclear waste and recovering radioactive strontium resources. Metal–organic frameworks (MOFs) are potential materials for the separation of aqueous metal ions owing to their designable structure and tunable functionality. Herein, a novel 3D MOF material MOF‐18Cr6, in which 1D channels are formed using 18‐crown‐6‐ether‐containing ligands as channel walls, is fabricated for strontium(II) separation. In contrast to traditional MOFs designed by grafting functional groups in the framework pores, MOF‐18Cr6 possesses regular 18‐crown‐6‐ether cavities on the channel walls, which not only can transport and intake strontium(II) via the channels, but also prevent blockage of the channels after the binding of strontium(II). Consequently, the functional sites are fully utilized to achieve a high strontium(II) removal rate of 99.73 % in simulated nuclear wastewater. This study fabricates a highly promising adsorbent for the separation of aqueous radioactive strontium(II), and more importantly, can provide a new strategy for the rational design of high‐performance MOF adsorbents for separating target substances from complex aqueous environments.

Facile synthesis of 2D bimetallic MOF micro/nanostructures for enhanced supercapacitor

The two-dimensional (2D) metal-organic framework (MOF) micro/nanostructures have emerged as promising materials for energy storage. Herein, we report a facile synthesis of 2D CoNi(x:y)-MOFs (x:y = 1:0, 1:2, 1:4, 1:6, 1:8, 1:10 and 0:1) via simple stirring reaction of metal salts (CoCl2·6H2O and/or NiCl2·6H2O) and biphenyldicarboxylate (H2BPDC) with the assistance of appropriate content of triethylamine and water. Water not only promotes trimethylamine to deprotonate the carboxylic acid to participate in coordination but also enables trimethylamine to generate hydroxide ions, affecting the composition and microstructure of the products. Compared with Co-MOF, Ni-MOF, and bulk CoNi(1:6)-MOF, the 2D CoNi(1:6)-MOF delivers higher specific capacitance of 455 F g−1/246C g−1 at 0.5 A g−1 owing to its optimal Co/Ni co-doping and unique 2D micro/nanostructure. In addition, the assembled CoNi(1:6)-MOF//AC exhibits high specific capacitance and a maximum energy density of 38.8 Wh kg−1 at a power density of 263.3 W kg−1.

Realization of high-order topological phase transition in 2D metal-organic frameworks

In two-dimensional (2D) scale, controllable topological phase transition between a conventional topological quantum state and a higher-order one has been a challenge currently. Herein, based on first-principles, we report 2D metal-organic frameworks (MOFs) are ideal choice for realizing such topological phase transition. Taking MOF candidate Pd3(C6S6)2 as an example, a semimetallic band structure is present at the equilibrium state. Under moderate compressive strain, it features a nontrivial energy gap and corner states, which is evidenced as a second-order topological insulator (SOTI). In addition, the band order for its low-energy bands switches at moderate tensile strain, during which topological phase transition from SOTI and topological semimetal to double Weyl semimetal (DWSM) happens, accompanied by the change in real Chern number form to . At the critical point for the phase transition, the system can be characterized as a 2D pseudospin-1 fermion. Beside Pd3(C6S6)2, we further identify the ferromagnetic monolayer Fe3(C6S6)2 can also take the DWSM-to-SOTI phase transition, where the topological fermions and corresponding edge/corner states could be fully spin-polarized. This work has for the first time realized topological transition between conventional topological quantum state and a higher-order one in both nonmagnetic and magnetic MOFs.

Syntheses, Crystal Structures, and Catalytic Properties of Three Cu(II) and Cobalt(II) Coordination Compounds Based on an Ether-Bridged Tetracarboxylic Acid.

Three new products, [Cu2(μ3-dppa)(2,2'-bipy)2(H2O)]n·2nH2O (1), [Co4(μ4-dppa)2(phen)4(H2O)4]·2H2O (2), and [Co2(μ6-dppa)(μ-4,4'-bipy)(H2O)2]n·3nH2O (3) were synthesized using a hydrothermal method from Cu(II) and Co(II) metal(II) chlorides, 3-(3,4-dicarboxyphenoxy)phthalic acid (H4dppa), and different auxiliary ligands, namely 2,2'-bipyridine (2,2'-bipy),1,10-phenanthroline (phen), and 4,4'-bipyridine (4,4'-bipy). Products 1-3 were characterized by elemental analysis, FTIR, TGA, PXRD, SEM, and single-crystal X-ray crystallography. The structure of 1 features a 1D chain of the 2C1 topological type. Compound 2 shows a discrete tetrameric complex. Product 3 demonstrates a 3D metal-organic framework (MOF) with the new topology. Their structure and topology, thermal stability, and catalytic activity were studied. In particular, excellent catalytic activity was demonstrated for copper(II)-polymer 1 in the cyanosilylation reaction at 35 °C.

Facile synthesis of ZnCdS quantum dots via a novel photoetching MOF strategy for boosting photocatalytic hydrogen evolution

MOF self-sulfurizing is regarded as a promising approach for preparing quantum dots (QDs). Herein, ZnCdS QDs were constructed by photoetching self-sulfurization of a novel 3D metal–organic framework (namely PZH) for the first time. The results of the morphology and X-ray diffraction (XRD) characterizations show that the ZnCdS QDs do not self-aggregate, and the frame structure of PZH remain intact. Under visible-light irradiation, ZnCdS QDs/PZH with the photoetching time of 60 min (ZnCdS−3/PZH) exhibits a remarkably enhanced photocatalytic hydrogen production rate with an apparent quantum efficiency (AQE) of 18.51 % at 420 nm. The improvement of photocatalytic activity can be predominantly attributed to an outstanding four synergism of promoting separation and transfer of carriers owing to ZnCdS QDs shortening the charge transmission distance, inhibiting the recombination of photogenerated electron-holes of uniform dispersed quantum dots without aggregating, optimizing the adsorption behavior of the active intermediates (H*) owing to the synergistic action between ZnCdS QDs and PZH, offering more holes for reactant molecules transmission due to presence of PZH. The density functional theory (DFT) calculation reveals that ZnCdS quantum dots relative to large size S-ZnCdS is going to help reduce the Gibbs free energy of photocatalytic hydrogen evolution reaction. More importantly, this rare strategy not only flourish the design idea of quantum dots, but also promote the applications of MOF in photocatalytic H2 production.