Lithium film with abundant stepped structures: A promising route for homogeneous Li ion deposition to conquer lithium dendrite issue and its action mechanism

Lithium is considered to be the ‘‘holy grail” for the application of energy storage due to its highest theoretical capacity and lowest anode potential. However, one of the grand difficulties in the development of lithium-based batteries is the lithium dendrite growth that leads to capacity fading and electrode degradation over long-term cycling. Compared with conventional electrolyte modifications, artificial solid electrolyte interfaces(SEI) synthesis and framework designing approaches, tuning surface morphology of lithium anode is the direct route to induce homogeneous Li ion deposition. Due to the high chemical activity of lithium metal, however, controllable growth of lithium micro/nanostructures by traditionally chemical approaches is still a big challenge. Herein, we have developed a facile compression route to fabricate lithium anode with abundant stepped lithium structures. The electrochemical results demonstrate that the dendritic growth issue is effectively suppressed by orderly arranged stepped lithium structures. After 90 cycles, a high discharge capacity of 954 mAh g^(-1) is achieved, which is 2.7times that of the uncompressed lithium anode(342 mAh g). First-principles calculations reveal that the orderly arranged stepped lithium structures are lithiophilic active sites to adsorb Li ion, which contributes to homogeneous deposition of Li ion on lithium anode, eventually solving the lithium dendrite issue. This work paves a new road to suppress dendritic growth, which will provide some new ideas to design long recycling sodium, potassium and zinc, and other metal anode batteries.

Novel ABCB4 mutations in an infertile female with progressive familial intrahepatic cholestasis type 3:A case report

BACKGROUND Mutations that occur in the ABCB4 gene,which encodes multidrug-resistant protein 3,underlie the occurrence of progressive familial intrahepatic cholestasis type 3(PFIC3).Clinical signs of intrahepatic cholestasis due to gene mutations typically first appear during infancy or childhood.Reports of PFIC3 occurring in adults are rare.CASE SUMMARY This is a case study of a 32-year-old infertile female Chinese patient with a 15-year history of recurrent abnormal liver function.Her primary clinical signs were elevated levels of alkaline phosphatase andγ-glutamyl transpeptidase.Other possible reasons for liver dysfunction were eliminated in this patient,resulting in a diagnosis of PFIC3.The diagnosis was confirmed using gene detection and histological analyses.Assessments using genetic sequencing analysis indicated the presence of two novel heterozygous mutations in the ABCB4 gene,namely,a 2950C>T;p.A984V mutation(exon 24)and a 667A>G;p.I223V mutation(exon 7).After receiving ursodeoxycholic acid(UDCA)treatment,the patient's liver function indices improved,and she successfully became pregnant by in vitro fertilization.However,the patient developed intrahepatic cholestasis of pregnancy in the first trimester.Fortunately,treatment with UDCA was safe and effective.CONCLUSION These novel ABCB4 heterozygous mutations have a variety of clinical phenotypes.Continued follow-up is essential for a comprehensive understanding of PFIC3.

Efficient CO_(2) photoreduction enabled by the energy transfer pathway in metal-organic framework

Many studies in metal-organic frameworks(MOFs)aiming for high photocatalytic activity resort to self-assembling both energy donor and acceptor building units in skeleton to achieve effective energy transfer,which,however,usually needs tedious synthetic procedure and design of a new MOF.In this work,we demonstrated that building a Förster resonance energy transfer(FRET)pathway can be realized through suitable molecular doping in a given MOF structure without altering the original porous structure,presenting an alternative strategy to design efficient photocatalysts for CO_(2)reduction.In situ electron spin resonance,ultrafast transient absorption spectroscopy,and computational studies reveal that the FRET-induced excitation has dramatically altered the exciton transfer pathway in structure and facilitated electron-hole separation.As a result,the molecular doped MOFs synthesized through one-pot reaction show outstanding selectivity(96%)and activity(1314μmol⋅g^(−1)⋅h^(−1))for CO production versus almost no activity for the pristine MOFs,and this result stands out from existing competitors.Furthermore,the reaction mechanism was proposed and the intermediate signals were detected by in situ diffuse reflectance infrared Fourier transform spectroscopies.This study presents a clear picture of building FRET process in MOFs through molecular doping and provides a new design strategy for MOF-based photocatalysts.

Post-modification of metal-organic framework for improved CO_(2) photoreduction efficiency

Utilizing metal-organic frameworks(MOFs) to design photocatalysts for CO_(2) reduction catalysts is an excellent idea but currently restricted by the relatively low activity. Enhancing CO_(2) affinity and tuning the oxidation state of metal clusters in MOFs might be a solution to improve the catalytic performance.Herein, the Cl-bridge atoms in the metal clusters of a cobalt MOF were easily exchanged with OH-,which simultaneously oxidized a portion of Co(Ⅱ) to Co(Ⅲ) and resulted in a much enhanced photocatalytic activity for CO_(2) reduction. In contrast, the original framework does not exhibit such superior activity. Comprehensive characterizations on their physicochemical properties revealed that the introduction of hydroxyl group not only greatly increases the CO_(2) affinity but also alters the oxidation state of metal clusters, resulting in significantly improved photocatalytic activities for CO_(2) reduction. This work provides important insight into the design of efficient photocatalysts.

Structure and magnetic property of bimetallic hexanuclear cluster based on 5-chlorosalicylaldehyde oxime

The bimetallic hexanuclear cluster [Mn4Ni2O2（Cl-Sao）6.（CH3OH）8].10CH3OH （1） was synthesized. Single-crystal X-ray analysis reveals that 1 consists of two [Mn2Ni（μ3-O）（Cl-Sao）3] subunits linked together via two pairs of long Ni-O bonds involving two oximate oxygen atoms and two phenolate oxygen atoms. Each Mn and Ni center achieves six-coordination with axial methanol molecules. The spin centers of the Mnm and Niu ions exchange magnetic coupling through O2-, O-phenolate and -N-O- bridges. The magnetic properties of the cluster have been investigated.

Designing a Bifunctional Brønsted Acid-Base Heterogeneous Catalyst Through Precise Installation of Ligands on Metal-Organic Frameworks

A Brønsted acid-base bifunctional metal-organic framework(MOF)catalyst,PCN-700-AB[A=Brønsted acid site,TPDC-(COOH)_(2)[(1,1′∶4′,1″-terphenyl)-2,2″,4,4″-tetracarboxylic acid]and B=Brønsted basic site,BDC-NH_(2)],was designed precisely and synthesized successfully through sequential installation of Brønsted acid and base functionalities in a crystalline zirconium(Zr)-MOF.The installation underwent single-crystal-to-singlecrystal transformation throughout the process;hence,the structure of the bifunctional catalyst could be characterized accurately via single-crystal X-ray crystallography.The bifunctional MOF catalyst obtained exhibited excellent acid-base catalytic activity for a cascade of one-pot deacetalization-Knoevenagel condensation reaction.The work presented here could be considered as a promising solution to incorporate multifunctional components readily,especially the hostile aspects,into one MOF structure.

Precise Construction of Stable Bimetallic Metal–Organic Frameworks with Single-Site Ti(IV) Incorporation in Nodes for Efficient Photocatalytic Oxygen Evolution

Assembling the reactive low-cost Co clusters and photoresponsive ligands in the form of metal–organic frameworks(MOFs)is a promising strategy to construct efficient water-oxidizing photocatalysts,but it is restricted by poor water stability.Introducing high valent cations in the clusters to build heterometallic Co-MOFs might be a solution,yet a precise fabrication strategy is still challenging.

Harnessing Electrostatic Interactions for Enhanced Conductivity in Metal-Organic Frameworks

The poor electrical conductivity of metal-organic frameworks(MOFs)has been a stumbling block for its applications in many important fields.Therefore,exploring a simple and effective strategy to regulate the conductivity of MOFs is highly desired.Herein,anionic guest molecules are incorporated inside the pores of a cationic MOF(PFC-8),which increases its conductivity by five orders of magnitude while maintaining the original porosity.In contrast,the same operation in an isoreticular neutral framework(PFC-9)does not bring such a significant change.Theoretical studies reveal that the guest molecules,stabilized inside pores through electrostatic interaction,play the role of electron donors as do in semiconductors,bringing in an analogous n-type semiconductor mechanism for electron conduction.Therefore,we demonstrate that harnessing electrostatic interaction provides a new way to regulate the conductivity of MOFs without necessarily altering the original porous structure.This strategy would greatly broaden MOFs’application potential in electronic and optoelectronic technologies.

Harnessing Electrostatic Interactions for Enhanced Conductivity in Metal-Organic Frameworks

The poor electrical conductivity of metal-organic frameworks(MOFs)has been a stumbling block for its applications in many important fields.Therefore,exploring a simple and effective strategy to regulate the conductivity of MOFs is highly desired.Herein,anionic guest molecules are incorporated inside the pores of a cationic MOF(PFC-8),which increases its conductivity by five orders of magnitude while maintaining the original porosity.In contrast,the same operation in an isoreticular neutral framework(PFC-9)does not bring such a significant change.Theoretical studies reveal that the guest molecules,stabilized inside pores through electrostatic interaction,play the role of electron donors as do in semiconductors,bringing in an analogous n-type semiconductor mechanism for electron conduction.Therefore,we demonstrate that harnessing electrostatic interaction provides a new way to regulate the conductivity of MOFs without necessarily altering the original porous structure.This strategy would greatly broaden MOFs’application potential in electronic and optoelectronic technologies.

Building Block Symmetry Relegation Induces Mesopore and Abundant Open-Metal Sites in Metal-Organic Frameworks for Cancer Therapy

The judicious choice of metal clusters and organic building blocks leads to a wide variety of structures for metal–organic frameworks(MOFs).In this work,we demonstrated that relegating the symmetry of a building block can also lead to the proliferation of new MOF structures.Herein,a triangle building block was elongated with reduced symmetry for MOF construction,which gave rise to a novel(3,4,6)-connected idp(based on the definition of Reticular Chemistry Structure Resource,http://rcsr.net/)network(PFC-16)with mesopores and abundant open-metal sites.The framework is composed of the rarely observed tetrakis hexahedral cages,surrounding which are small cages arranged in sodalite topology.The relegated symmetry was required for this novel self-assembly.The obtained MOF with mesopores,a robust backbone,and abundant open-metal sites can incorporate functional species in the structure,which is representatively demonstrated by internalizing the photosensitizer zinc(II)phthalocyanine(ZnPc)and the modifying tumor-targeting molecule folic acid(FA)in PFC-16.The obtained composite FA-ZnPc@nano-PFC-16 shows excellent photodynamic therapy(PDT)efficiency for both in vitro and in vivo experiments,representing a promising candidate for cancer therapy.

Stable hydrogen-bonded organic frameworks and their photo-and electro-responses

Hydrogen-bonded organic frameworks(HOFs)are a recent class of porous materials that have garnered considerable research interest owing to their distinctive characteristics.HOFs can be constructed through judicious selection of H-bonding motifs,which are further enforced by other weak intermolecular interactions such asπ–πstacking,van der Waals forces,and framework interpenetration.Taking advantage of these interactions,we can expand the functional field of HOFs by introducing active molecules.Recently,researchers have made substantial advancements in using HOFs for chemical sensing,catalysis,proton conduction,biological applications,and others.The low bonding energy of H-bonds allows for precise control over the concentration of ligands in solvents,forming diverse HOF structures.These varied structures offer significant advantages for producing HOFs with photo-responsive and electro-responsive properties.However,the presence of H-bonds in HOFs results in their inherent lower stability compared to metal-organic frameworks(MOFs)and covalent-organic frameworks(COFs)formed via coordination and covalent bonds,respectively.As a result,the pursuit of stable and innovative HOF materials with novel functional sites remains an ongoing challenge.This review provides an overview of recent research progress in the development of new strategies for stable HOF synthesis and applications of HOFs with stimuli-responsive properties.We first classified all synthetic methods reported to date and discussed the stable HOFs synthesized,as well as their unique properties and applications.In addition,we summarized the applications of HOFs utilizing their synergistic responses to external stimuli,including photo,electrical,pressure,and chemical stimuli.We systematically reviewed stable HOF synthesis and applications,which may lead to a deeper understanding of the structure–activity relationship for these materials and guide future HOF design.