Atomically Dispersed Ruthenium Catalysts with Open Hollow Structure for Lithium-Oxygen Batteries

Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.

Remote Stereocontrol of All-Carbon Quaternary Centers via Cobalt-Catalyzed Asymmetric Olefin Isomerization

Asymmetric olefin isomerization has become a powerful tool for positional migration of C=C double bonds to afford valuable chiral olefins.However,the synthesis of optically active all-carbon quaternary stereocenters via this strategy is still rare.Herein,we report a cobaltcatalyzed desymmetric olefin isomerization to access 1-methylcyclohexenes bearingβ-quaternary stereocenters in a chemo-,site-,and stereoselective fashion.Preliminary mechanistic studies have revealed the Co-H insertion/β–Helimination reaction pathway and the origin of remote stereocontrol of all-carbon quaternary centers.The gram-scale synthesis and stereoretentive transformations of spirocyclic products demonstrate the synthetic utility of this reaction.

Engineering Mechanical Strong Biomaterials Inspired by Structural Building Blocks in Nature

The intricate multiscale architectures in natural structural building blocks provide many sources of inspiration for the designs of artificial biomaterials.In nature,the assembly of highly ordered molecular crystals and amorphous aggregates often derives from inter-and intra-molecular interactions of biomacromolecules,e.g.,proteinaceous materials.The structural biomaterials derived from the protein self-assembly behave with remarkable mechanical performance.However,there is still a grand challenge to mimic the mechanical properties of natural protein-based biomaterials in a rational design fashion to yield comparable man-made synthetic ensembles.In this review,a brief perspective on current challenges and advances in terms of bioinspired structural materials is presented.We outline a framework for mimicking protein self-assembly of natural building blocks across multiscale and highlight the critical role of synthetic biology and chemical modifications in material biosynthesis.Particularly,we focus on the design and promising applications of protein-based fibers,adhesives,dynamic hydrogels and engineered living materials,in which natural mechanical functions are effectively reproduced.

用于实时皮肤创面愈合的超强工程化蛋白凝聚体黏合剂

Adhesives have attracted a great deal of attention as an advanced modality in biomedical engineering because of their unique wound management behavior.However,it is a grand challenge for current adhesive systems to achieve robust adhesion due to their tenuous interfacial bonding strength.Moreover,the absence of dynamic adaptability in conventional chemical adhesives restricts neoblasts around the wound from migrating to the site,resulting in an inferior tissue-regeneration effect.Herein,an extracellular matrix-derived biocomposite adhesive with robust adhesion and a real-time skin healing effect is well-engineered.Liquid–liquid phase separation is well-harnessed to drive the assembly of the biocomposite adhesive,with the active involvement of supramolecular interactions between chimeric protein and natural DNA,leading to a robustly reinforced adhesion performance.The bioadhesive exhibits outstanding adhesion and sealing behaviors,with a sheared adhesion strength of approximately 18 MPa,outperforming its reported counterparts.Moreover,the engineered bioderived components endow this adhesive material with biocompatibility and exceptional biological functions including the promotion of cell proliferation and migration,such that the use of this material eventually yields real-time in situ skin regeneration.This work opens up novel avenues for functionalized bioadhesive engineering and biomedical translations.

Optimal geometrical configuration and oxidation state of cobalt cations in spinel oxides to promote the performance of Li-O_(2) battery

Co_(3)O_(4) is considered as one of promising cathode catalysts for lithium oxygen(Li-O_(2))batteries,which contains both tetrahedral Co^(2+)sites(Co^(2+)Td)and octahedral Co^(3+)sites(Co^(3+)Oh).It is important to reveal the effect of optimal geometric configuration and oxidation state of cobalt ion in Co_(3)O_(4) to improve the performance of Li-O_(2) batteries.Herein,through regulating the synthesis process,Co^(2+)and Co^(3+)sites in Co_(3)O_(4) were replaced with Zn and Al atoms to form materials with a unique Co site.The Li-O_(2) batteries based on ZnCo_(2)O_(4) showed longer cycle life than that of CoAl_(2)O_(4),suggesting that in Co_(3)O_(4),the Co^(3+)Oh site is a relatively better geometric configuration than Co^(2+)Td site for Li-O_(2) batteries.Theoretical calculations revealed that Co^(3+)Oh sites provide higher catalysis activity,regulating the adsorption energy of the intermediate LiO_(2) and accelerating the kinetics of the reaction in batteries,which further leads to the change of the morphology of the discharge product and ultimately improves the electrochemical performance of the batteries.

Manipulating guest-responsive spin transition to achieve switchable fluorescence in a Hofmann-type framework

The change of fluorescence emission manipulated by spin state transition attracts considerable attention owing to its potential applications in magneto-optical switching devices.Herein,we report two two-dimensional(2D)Hofmann-type spin crossover(SCO)metal-organic frameworks(MOFs)[Fe^(Ⅱ)(PNI)_(2){Ag^(Ⅰ)(CN)_(2)}_(2)]·CHCl_(3)(3Ag·CHCl_(3))and[FeⅡ(PNI)_(2){AuⅠ(CN)_(2)}_(2)]·CHCl_(3)(3Au·CHCl_(3))based on the fluorescent ligand N-(4-pyridylmethyl)-1,8-naphthalimide(PNI).Both complexes exhibit interesting SCO behaviors switched by guest solvent molecules,namely three-step transitions for the solvated complexes and complete onestep hysteretic SCO for the desolvated ones,verified by temperature-dependent magnetic susceptibility measurements,Mossbauer spectra,structural analyses,and differential scanning calorimetry measurements.Correspondingly,temperature-dependent fluorescence spectra exhibit double peaks(monomer and excimer emission)with both emission peaks change consistent with the change in SCO properties during the solvent molecule removal.In this study,we integrated guest-responsive SCO behavior into MOFs to manipulate the multistability of spin state and fluorescence switching,providing a rational strategy for the development of stimuli-responsive multifunctional materials.

Translucent ceramic enabling next-generation lasing-driven near-infrared light source

Broadband near-infrared(NIR) light sources demonstrate great potential in quantitative food analysis, material identification,invasive brain imaging diagnosis, and real-time health monitoring fields, etc. [1–3]. Compared with competing technologies based on quantum dots and organic crystals, NIR-emitting phosphor converted light-emitting diodes(pc-LEDs) favor high spectral modulation and physicochemical stability [4].

Recent Progress in Electrocatalytic Conversion of Lignin:From Monomers,Dimers,to Raw Lignin

Lignin,as the second largest renewable biomass resource in nature,has increasingly received significant interest for its potential to be transformed into valuable chemicals,potentially contributing to carbon neutrality.Among different approaches,renewable electricity-driven biomass conversion holds great promise to substitute a petroleum resource-driven one,owing to its characteristics of environmental friendliness,high energy efficiency,and tunable reactivity.The challenges lie on the polymeric structure and complex functional groups in lignin,requiring the development of efficient electrocatalysts for lignin valorization with enhanced activity and selectivity toward targeted chemicals.In this Review,we focus on the advancement of electrocatalytic valorization of lignin,from monomers,to dimers and to raw lignin,toward various valueadded chemicals,with emphasis on catalyst design,reaction innovation,and mechanistic study.The general strategies for catalyst design are also summarized,offering insights into enhancing the activity and selectivity.Finally,challenges and perspectives for the electrocatalytic conversion of lignin are proposed.

Phosphorus induced activity-enhancement of Fe-N-C catalysts for high temperature polymer electrolyte membrane fuel cells

Fe-N-C materials with atomically dispersed Fe–N_(4) sites could tolerate the poisoning of phosphate,is regarded as the most promising alternative to costly Pt-based catalysts for the oxygen reduction in high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs).However,they still face the critical issue of insufficient activity in phosphoric acid.Herein,we demonstrate a P-doping strategy to increase the activity of Fe-N-C catalyst via a feasible one-pot method.X-ray absorption spectroscopy and electron microscopy with atomic resolution indicated that the P atom is bonded with the N in Fe–N_(4) site through C atoms.The as prepared Fe-NCP catalyst shows a half-wave potential of 0.75 V(vs.reversible hydrogen electrode(RHE),0.1 M H_(3)PO_(4)),which is 60 and 40 mV higher than that of Fe-NC and commercial Pt/C catalysts,respectively.More importantly,the Fe-NCP catalyst could deliver a peak power density of 357 mW·cm^(−2)in a high temperature fuel cell(160℃),exceeding the non-noble-metal catalysts ever reported.The enhancement of activity is attributed to the increasing charge density and poisoning tolerance of Fe–N_(4) caused by neighboring P.This work not only promotes the practical application of Fe-N-C materials in HT-PEMFCs,but also provides a feasible P-doping method for regulating the structure of single atom site.

Preparation of Photo-responsive DNA Supramolecular Hydrogels and Their Application as UV Radiometers

Ultraviolet light(UV)is an essential component of ambient light,but high dose UV would damage genome DNA.While semiconductors and soft materials have been employed to detect the UV,the complex process and the instrumental requirement have limited the application in daily life.In this study,taking advantage of sequence designability,a series of hydrogels with different gel-sol transition rates was constructed under the same UV intensity by introducing competing hybridization to tune the stability of the molecular network.Through estimating the transition time between each system under UV light irradiation,the intensity of UV could be roughly estimated,which provided a convenient method for the visual detection of UV.

Revealing the Flexibility of Inorganic Sub-Nanowires by Single-Molecule Force Spectroscopy

Sub-nanowires(SNWs),∼1 nm in thickness,possess an inorganic skeleton but display characteristics akin to those of carbon–carbon backbone polymers,such as flexibility,adhesion,gelation,self-assembling behaviors,and shear-thinning properties.Despite this,the underlying mechanism for these polymer-like properties remains unexplored.This study investigates the origin of SNWs’unique behavior from three distinct perspectives.Utilizing single-molecule force spectroscopy,we quantitatively measure the persistence lengths of SNWs,which provide a measure of flexibility.In addition,we evaluate the macroscopic mechanical properties of SNW materials,including the strength of electrospun fibers and gelation in solutions.Finally,we apply molecular dynamics to simulate the behaviors of SNWs under elongating and rotating conditions.The three perspectives mentioned above in the study collectively provide evidence for the structure-activity relationship of nanomaterials:a freely rotated backbone results in a flexible SNW,which is inclined to bend and entangle to form gels in solutions.Conversely,a stiff backbone leads to a rigid SNW,which induces strong fibers.

Engineered spidroin-derived high-performance fibers for diverse applications

Spider silks are well known for their exceptional mechanical properties that are tougher than Kevlar and steel.However,the restricted production amounts from their native sources limit applications of spider silks.Over the decades,there have been significant interests in fabricating man-made silk fibers with comparable performance to natural silks,inspiring many efforts both for biosynthesizing recombinant spider silk proteins(spidroins)in amenable heterologous hosts and biomimetic spinning of artificial spider silks.These strategies provide promising routes to produce high-performance and functionally optimized fibers with diverse applications.Herein,we summarize the hosts that have been applied to produce recombinant spidroins.In addition,the fabrication and mechanical properties of recombinant spidroin fibers and their composite fibers are also introduced.Furthermore,we demonstrate the applications of recombinant spidroin-based fibers.Finally,facing the challenges in biosynthesis,scalable production,and hierarchical assembly of high-performance recombinant spidroins,we give a summary and perspective on future development.

基于微生物的稀土材料制备

稀土元素(REEs)作为现代高科技产业发展的关键原材料,在多个前沿领域具有广泛应用.然而,由于稀土元素分布相对分散,其提取往往伴随着环境退化.此外,稀土元素的相似化学性质导致了分离过程中的高能耗和过度污染排放.为了实现稀土的绿色发展和高效资源利用,通过合成生物学技术构建了工程稀土微生物.此外,我们建立了工程稀土微生物合成平台,实现了原位合成高附加值的稀土生物材料,推动了临床转化研究和应用的进展.本文综述了稀土微生物的合理设计、高价值稀土生物材料的合成及其应用.最后,简要讨论了该领域的未来研究和发展前景.

Lanthanide-based microlasers:Synthesis,structures,and biomedical applications

The large size of lasers limits their applications in confined spaces,such as in biosensing and in vivo brain tissue imaging.In this regard,micron-sized lasers have been developed.They exhibit great potential for biological detecting,remote sensing,and depth tracking due to their small sizes,sensitive properties of their spectral fingerprints,and flexible positional modulation in the microenvironment.Lanthanide-based luminescent materials that possess long excited-state lifetime,narrow emission bandwidth,and upconversion behaviors are promising as gain mediums for novel microlasers.In addition,lanthanide-based microlasers could be generated under natural ambient conditions with pumped or continuous light sources,which significantly promotes the practical applications of microlasers.Recent progress in the design,synthesis,and biomedical applications of lanthanide-based microlasers has been outlined in this review.Lanthanide ions doped and upconverted lanthanide-based microlasers are highlighted,which exhibit advantageous structures,miniaturized dimensions,and high lasing performance.The applications of lanthanide-based microlasers are further discussed,the upconverted microlasers show great advantages for biological applications owing to their tunable excitation and emission characteristics and excellent environmental stability.Moreover,perspectives and challenges in the field of lanthanide-based microlasers are presented.

SnIP-type atomic-scale inorganic double-helix semiconductors: Synthesis, properties, and applications

Flexible inorganic double helical semiconductors similar to DNA have fueled the demand for efficient materials with innovative structures and excellent properties.The recent discovery of tin phosphide iodide(SnIP),the first carbon-free double helical semiconductor at an atomic level,has opened new avenues of research for semiconducting devices such as thermoelectric and sensor devices,solar cells,and photocatalysis.It has drawn significant academic attention due to its high structural flexibility,band gap in the visible spectrum range,and non-toxic elements.Herein,the recent progress in developing SnIP,including its prestigious structure,versatile and intriguing properties,and synthesis,is summarized.Other analogues of SnIP and SnIP-based hybrid materials and their applications in photocatalysis are also discussed.Finally,the review concludes with a critical summary and future aspects of this new inorganic semiconductor.

Hydrogen bond-bridged phosphorene flexible film for photodynamic inhibiting Staphylococcus aureus

Antibiotics are a widely used and effective treatment for bacterial infections.However,bacteria can gradually evolve during infection,leading to developing resistance to antibiotics,which renders previously effective treatments ineffective.Finding a useful and convenient manner to treat bacterial infections is a great challenge.Here,we report a flexible hydrogen-bond-bridged phosphorene film with photodynamic antibacterial properties and excellent mechanical properties,fabricated from electrochemical exfoliation of black phosphorus(BP).When illuminated under 700 nm light,the hydrogen bond-bridged phosphorene flexible film is capable of converting ground-state triplet oxygen(O_(2))into excited-state singlet oxygen(^(1)O_(2)),destroying the structure of the membrane of Staphylococcus aureus,and eventually leading to bacterial death,via breaking the C=C of unsaturated fatty acids within the bacterial cell membrane after the reaction between^(1)O_(2)and unsaturated fatty acids,thus realizing a highly efficient antibacterial approach,which is supported by gas chromatography-mass spectrometry(GC-MS)technique.This work establishes an effective phototherapy platform for treating bacterial traumatic infections.

Atomically Dispersed Catalysts:Precise Synthesis,Structural Regulation,and Structure-Activity Relationship

Atomically dispersed catalysts(ADCs)have been diffusely researched for the development of advanced catalytic processes owing to their welldefined structure,high atomic utilization,and outstanding activity.Precisely decoding the intrinsic structures and coordination microenvironments of ADCs still confronts significant challenges.Overcoming these challenges is important for profound understanding of the structure-activity relationships and directing the future design of ADCs.Herein,this minireview summarizes recent progress and advanced characterization techniques for the engineering of ADCs,including single-atom catalysts,dualatom catalysts,and atomic cluster catalysts with regard to precise synthesis,structural regulation,and the structure-performance relationship.The catalytic merits and regulation strategies of recent breakthroughs in energy conversion,enzyme mimicry,and organic synthesis are thoroughly discussed to disclose the catalytic mechanism-guided ADCs design.Finally,a comprehensive summary of the future challenges and potential prospects is presented to stimulate more design and application possibilities for ADCs.We believe that this comprehensive minireview will open up novel pathways for the widespread utilization of ADCs in diverse catalytic processes.

A general and facile calcination method to synthesize single-site catalysts for highly efficient electrochemical CO_(2) reduction

The electrochemical CO_(2) reduction reaction(CO_(2)RR)has received widespread attention as a promising method for producing sustainable chemicals and mitigating the global warming.Here,we demonstrate a general and facile synthetic route for the metal-nitrogen-carbon(M-N-C)type catalyst by simply calcinating metal acetate and urea with commercial carbon black,which have potential application in CO_(2)RR.The synthesized Ni-NC-600 catalyst has the structure of single Ni atom coordinated with one N atom and three C atoms(Ni-N_(1)C_(3)),which is suggested by X-ray absorption spectroscopy.The Ni-NC-600 catalyst exhibits high CO_(2)RR catalytic performance and a high CO Faraday efficiency above 98%in a wide potential range from-0.7 to-1.3 V(vs.reversible hydrogen electrode(RHE)),superior to most of the reported Ni-N-C catalysts.This work has developed a facile strategy to synthesize high performance CO_(2)RR catalyst.

Charge-asymmetry Fe_(1)Cu single-atom alloy catalyst for efficient oxygen reduction reaction

The development of high-efficient and low-cost oxygen reduction reaction(ORR)electrocatalysts is crucial for the practical applications of metal-air batteries.One promising way is to develop Fe single-atom catalysts.However,the single active center and inherent electronic structure of Fe single-atom catalysts lead to the undesirable adsorption of multiple ORR intermediates.Herein,a charge-asymmetry single-atom alloy(SAA)catalyst with Fe-Cu dual sites supported on nitrogen-doped carbon nanosheet(Fe_(1)Cu SAA/NC)was constructed.Various characterizations manifest the existence of electron interaction between Fe and Cu in Fe_(1)Cu SAA/NC,which facilitates the adsorption of ORR intermediate for fast kinetics.Consequently,the charge-asymmetry Fe_(1)Cu SAA/NC exhibits much faster ORR kinetics with a half-wave potential of 0.917 V vs.reversible hydrogen electrode(RHE),outperforming its counterparts in the references.Furthermore,Fe_(1)Cu SAA/NC still maintains a high half-wave potential with only a drop of 5 mV after 5000 cycles,indicating excellent stability.This work provides a new strategy to design highly active and non-noble metal ORR electrocatalysts,which hold great potential for various catalytic applications.

Carbon-based supports for the electrocatalysis under industrially relevant conditions

1 Introduction.Carbon materials are ideal catalyst supports for functional metal components due to their appropriate physicochemical characteristics,such as high surface areas,tunable pore structures,variable morphologies and versatile surface properties based on chemical modifications,low cost and facile preparations from diverse precursors[1,2].