Metal-organic framework-derive d carbon-base d composites for electromagnetic wave absorption:Dimension design and morphology regulation

Developing highly efficient microwave absorbing materials(MAMs)to ameliorate the electromagnetic(EM)response and facilitate energy absorption is crucial in both the civil and military industries.Metal-organic framework(MOF)derived nanoporous carbon composites have emerged as advanced MAMs ow-ing to their rich porosity,tunable compositions,facile functionalization,and morphology diversity.To-gether with the flourishing development of composition-tuning strategy,the rational dimension design and elaborate control over the architectures have also evolved into an effective approach to regulating their EM properties.Herein,we provide a comprehensive review of the recent advances in using di-mension and morphology modulation to adjust the microwave attenuation capacities for MOF-derived carbon composites.The underlying design rules and unique advantages for the MAMs of various dimen-sions were discussed with the selection of representative work,providing general concepts and insight on how to efficiently tune the morphologies.Accordingly,the fundamental dimension-morphology-function relationship was also elucidated.Finally,the challenges and perspectives of dimension design and mor-phology control over MOF-derived MAMs were also presented.

Enhancing efficiency and stability of organic solar cells through a simplified four-step synthesis of fully non-fused ring electron acceptor

Design and synthesis of superior cost-effective non-fullerene acceptors(NFAs)are still big challenges for facilitating the commercialization of organic solar cells(OSCs),yet to be realized.Herein,two medium bandgap fully non-fused ring electron acceptors(NFREAs,medium bandgap,i,e.,1,3-1,8 eV),namely PTR-2Cl and PTR-4Cl are synthesized with only four steps by using intramolecular noncovalent interaction central core,structured alkyl side chain orientation linking units and flanking with different electron-withdrawing end group.Among them,PTR-4C1 exhibits increased average electrostatic potential(ESP)difference with polymer donor,enhanced crystallinity and compactπ-πstacking compared with the control molecule PTR-2CI.As a result,the PTR-4Cl-based OSC achieved an impressive power conversion efficiency(PCE)of 14.72%,with a much higher open-circuit voltage(V_(OC))of 0.953 V and significantly improved fill factor(FF)of 0.758,demonstrating one of the best acceptor material in the top-performing fully NFREA-based OSCs with both high PCE and V_(OC).Notably,PTR-4Cl-based cells maintain a good T_80lifetime of its initial PCE after over 936 h under a continuous thermal annealing treatment and over1300 h T_(80)lifetime without encapsulation.This work provides a cost-effective design strategy for NFREAs on obtaining high V_(OC),efficient exciton dissociation,and ordered molecular packing and thus high-efficiency and stable OSCs.

Hydrochloric acid‐mediated synthesis of ZnFe_(2)O_(4) small particle decorated one‐dimensional Perylene Diimide S‐scheme heterojunction with excellent photocatalytic ability

The recyclable and stable ZnFe_(2)O_(4) small particle decorated one‐dimensional perylene diimide(PDI)S‐scheme heterojunction(1D PDI/ZnFe_(2)O_(4))is prepared by the hydrochloric acid‐mediated(HCl‐mediated)strategy,interestingly,the morphology of the 1D PDI/ZnFe_(2)O_(4) can also be effectively regulated by HCl‐mediated process,the existence of HCl can regulate PDI into a uniform rod structure,while the co‐existence of HCl and PDI can limit ZnFe_(2)O_(4) to become the uniform small particles.More importantly,based on the 1D rod structure of PDI and the small size effect of ZnFe_(2)O_(4),carriers can migrate to the surface more easily,which can improve the photocatalytic activity.Meanwhile,due to the appropriate energy level structure,the S‐scheme heterojunction structure is formed between PDI and ZnFe_(2)O_(4),which eliminates meaningless photo‐generated charge carriers through recombination and introduces strong redox to further enhance the photodegradation effect,thereby,1D PDI/ZnFe_(2)O_(4) exhibits excellent photocatalytic ability,under the visible light irradiation,the degradation rate of tetracycline(TC)with 1D PDI/ZnFe_(2)O_(4)(66.67%)is 9.18 times that with PDI(7.26%)and 9.73 times that with ZnFe_(2)O_(4)(6.85%).This work proposes new ideas for the assembly of magnetic organic‐inorganic S‐scheme heterojunction photocatalysts.

Oxygen-doped Carbon Nitride Nanocages with Efficient Photon-to-Electron Conversion for Selective Oxidation of Xylose/Xylan to Yield Xylonic Acid

Highly efficient photon-to-electron conversion is crucial for achieving photocatalytic conversion.In this study,oxygen-doped carbon nitride nanocages(O@CNNCs)were engineered via dual strategies of morphology-controlled heteroatom doping,which was successfully used in the photocatalytic selective oxidation of xylose/xylan to xylonic acid.The nanocage-shaped O@CNNCs had a larger surface area,which was 4.02 times of carbon nitride(CN).Furthermore,with the assistance of morphology regulation and O-doping,O@CNNCs exhibit highly efficient photon-to-electron conversion,enhanced visible-light utilization,high photocurrent,low resistance,and fast separation/migration of electron-hole pairs.Correspondingly,the photocatalytic oxidation of xylose to xylonic acid using O@CNNCs was successfully achieved under mild reaction conditions with a yield of 83.4%.O@CNNCs have excellent recyclability,in which the yield of xylonic acid in the 5th cycle was 98.2%of its initial use.The O@CNNC photocatalytic system was also suitable for macromolecular xylan,and a xylonic acid yield of 77.34 mg was obtained when 100 mg xylan was used.The oxidation-active species captured experiments indicated that holes were crucial for the selective oxidation of xylose to xylonic acid.Overall,this study provides a new strategy for the preparation of photocatalysts with excellent photon-to-electron conversion and selective oxidation of biomass-derived feedstocks to xylonic acid.

Highly efficient ternary organic solar cells with excellent open-circuit voltage and fill factor via precisely tuning molecular stacking and morphology

The micro-morphology and molecular stacking play a key role in determining the charge transport process and nonradiative energy loss, thus impacting the performances of organic solar cells(OSCs). To address this issue, a non-fullerene acceptor PhC6-IC-F with alkylbenzene side-chain, possessing optimized molecular stacking, complementary absorption spectra and forming a cascade energy level alignment in the PM6:BTP-eC9 blend, is introduced as guest acceptor to improve efficiency of ternary OSCs. The bulky phenyl in the side-chain can regulate crystallinity and optimizing phase separation between receptors in ternary blend films, resulting in the optimal phase separations in the ternary films. As a result, high efficiencies of 18.33% as photovoltaic layer are obtained for PhC6-IC-F-based ternary devices with excellent fill factor(FF) of 78.92%. Impressively, the ternary system produces a significantly improved open circuit voltage(V_(oc)) of 0.857 V compared with the binary device,contributing to the reduced density of trap states and suppressed non-radiative recombination result in lower energy loss. This work demonstrates an effective approach for adjusting the aggregation, molecular packing and fine phase separation morphology to increase V_(oc) and FF, paving the way toward high-efficiency OSCs.

Regulate electric double layer for one-step synthesize and modulate the morphology of(oxy)hydroxides

FeOOH have received considerable attention due to their natural abundance and cost-effectiveness.Despite the significant progress achieved,the one-step synthesis of integrated FeOOH is still a major challenge.Meanwhile,the current research on FeOOH catalyst still suffers from the unclear mechanism of controlling morphology.Here,density functional theory(DFT)calculations and X-ray photoelectron spectroscopy(XPS)demonstrated the strong electron-capturing and hydrogen absorption ability of Co in FeOOH,which further promotes the formation and stabilization of FeOOH.We used a one-step electrodeposition method to synthesize Co introduced FeOOH integrated electrocatalyst and propose to introduce ions with different valence states to regulate the morphology of FeOOH by precise modulation of electric double layer(EDL)composition and thickness.The prepared Co-FeOOH-K^(+)has a larger electrochemically active surface area(ECSA)(325 cm^(2))and turnover frequency(TOF)value(0.75 s^(-1)).In the electrochemical experiments of an alkaline anion exchange membrane electrolyzer,Co-FeOOH-K^(+)shows better oxygen evolution performance than commercial RuO_(2) under industrial production conditions and has good industrial application prospects.

Filamentous morphology engineering of bacteria by iron metabolism modulation through MagR expression

The morphology is the consequence of evolution and adaptation.Escherichia coli is rod-shaped bacillus with regular dimension of about 1.5μm long and 0.5μm wide.Many shape-related genes have been identified and used in morphology engineering of this bacteria.However,little is known about if specific metabolism and metal irons could modulate bacteria morphology.Here in this study,we discovered filamentous shape change of E.coli cells overexpressing pigeon MagR,a putative magnetoreceptor and extremely conserved iron-sulfur protein.Comparative transcriptomic analysis strongly suggested that the iron metabolism change and iron accumulation due to the overproduction of MagR was the key to the morphological change.This model was further validated,and filamentous morphological change was also achieved by supplement E.coli cells with iron in culture medium or by increase the iron uptake genes such as entB and fepA.Our study extended our understanding of morphology regulation of bacteria,and may also serves as a prototype of morphology engineering by modulating the iron metabolism.

Synchronous regulation of morphology and electronic structure of FeNi-P nanosheet arrays by Zn implantation for robust overall water splitting

FeNi-based phosphides are one of the most hopeful electrocatalysts,whereas the significant challenge is to achieve prominent bifunctional catalytic activity with low voltage for water splitting.The morphology and electronic structure of FeNi-based phosphides can intensively dominate effective catalysis,therefore their simultaneous regulating is extremely meaningful.Herein,a robust bifunctional catalyst of Zn-implanted FeNi-P nanosheet arrays(Zn-FeNi-P)vertically well-aligned on Ni foam is successfully fabricated by Zn implanting strategy.The Zn fulfills the role of electronic donor due to its low electronegativity to enhance the electronic density of FeNi-P for optimized water dissociation kinetics.Meanwhile,the implantation of Zn into FeNi-P can effectively regulate morphology of the catalyst from thick and irregular nanosheets to ultrathin lamellar structure,which generates enriched catalytic active sites,leading to accelerating electron/mass transport ability.Accordingly,the designed Zn-FeNi-P catalyst manifests remarkable hydrogen evolution reaction(HER)activity with low overpotentials of 55 and 225 mV at 10 and 200 mA·cm^(−2),which is superior to the FeNi-P(82 mV@10 mA·cm^(−2)and 301 mV@200 mA·cm^(−2)),and even out-performing the Pt/C catalyst at a high current density>200 mA·cm^(−2).Moreover,the oxygen evolution reaction(OER)activity of Zn-FeNi-P also has dramatically improved(207 mV@10 mA·cm^(−2))comparable to FeNi-P(221 mV@10 mA·cm^(−2))and RuO_(2)(239 mV@10 mA·cm^(−2)).Noticeably,an electrolyzer based on Zn-FeNi-P electrodes requires a low cell voltage of 1.47 V to achieve 10 mA·cm^(−2),far beyond the catalytic activities of FeNi-P||FeNi-P(1.51 V@10 mA·cm^(−2))and the benchmark RuO_(2)||Pt/C couples(1.56 V@10 mA·cm^(−2)).This Zn-implanting strategy paves a new perspective for the development of admirable bifunctional catalysts.

Study on the morphological regulation mechanism of hollow silica microsphere prepared via emulsion droplet template

The morphology regulation of hollow silica microspheres is significant for their properties and applications. In this paper, hollow silica microspheres were formed through the hydrolysis and condensation reaction of tetraethyl orthosilicate(TEOS) at the interface of the emulsion droplet templates composed of liquid paraffin and TEOS, followed by dissolving paraffin with ethanol. The effects of various factors including the emulsifier structure and content, TEOS content, catalyst type, and the ethanol content in the continuous water phase on the particle size, shell thickness and morphology of the prepared hollow silica microspheres were studied in detail. The results show that the diffusion and contact of TEOS and water molecules as well as the hydrolysis condensation reaction of TEOS at the oil-water interface are two critical processes for the synthesis and morphological regulation of hollow silica microspheres. Cationic emulsifier with a hydrophobic chain of appropriate length is the prerequisite for the successful synthesis of hollow silica microspheres. The ethanol content in water phase is the dominant factor to determine the average diameter of hollow microspheres, which can vary from 96 nm to 660 nm with the increase of the volume ratio of alcohol-water from 0 to 0.7. The silica wall thickness varies with the content and the hydrophobic chain length of the emulsifier, TEOS content, and the activity of the catalyst. The component of the soft template will affect the morphology of the silica wall. When the liquid paraffin is replaced by cyclohexane, hollow microspheres with fibrous mesoporous silica wall are fabricated. This work not only enriches the basic theory of interfacial polymerization in the emulsion system, but also provides ideas and methods for expanding the morphology and application of hollow silica microspheres.

Construction of iron manganese metal-organic framework-derived manganese ferrite/carbon-modified graphene composites toward broadband and efficient electromagnetic dissipation

The preparation of carbon-based electromagnetic wave(EMW)absorbers possessing thin matching thickness,wide absorption bandwidth,strong absorption intensity,and low filling ratio remains a huge challenge.Metal-organic frameworks(MOFs)are ideal self-sacrificing templates for the construction of carbon-based EMW absorbers.In this work,bimetallic FeMn-MOF-derived MnFe_(2)O_(4)/C/graphene composites were fabricated via a two-step route of solvothermal reaction and the following pyrolysis treatment.The results re-veal the evolution of the microscopic morphology of carbon skeletons from loofah-like to octahedral and then to polyhedron and pomegran-ate after the adjustment of the Fe^(3+)to Mn^(2+)molar ratio.Furthermore,at the Fe^(3+)to Mn^(2+)molar ratio of 2:1,the obtained MnFe_(2)O_(4)/C/graphene composite exhibited the highest EMW absorption capacity.Specifically,a minimum reflection loss of-72.7 dB and a max-imum effective absorption bandwidth of 5.1 GHz were achieved at a low filling ratio of 10wt%.In addition,the possible EMW absorp-tion mechanism of MnFe_(2)O_(4)/C/graphene composites was proposed.Therefore,the results of this work will contribute to the construction of broadband and efficient carbon-based EMW absorbers derived from MOFs.

Over 16.7% efficiency of ternary organic photovoltaics by employing extra PC71BM as morphology regulator

Ternary organic photovoltaics(OPVs)are fabricated with PBDB-T-2 Cl:Y6(1:1.2,wt/wt)as the host system and extra PC71BM as the third component.The PBDB-T-2 Cl:Y6 based binary OPVs exhibit a power conversion efficiency(PCE)of 15.49%with a short circuit current(JSC)of 24.98 mA cm^-2,an open circuit voltage(VOC)of 0.868 V and a fill factor(FF)of 71.42%.A 16.71%PCE is obtained in the optimized ternary OPVs with PBDB-T-2 Cl:Y6:PC71BM(1:1.2:0.2,wt/wt)active layer,resulting from the synchronously improved JSC of 25.44 mA cm^-2,FF of 75.66%and the constant VOCof 0.868 V.The incorporated PC71BM may prefer to mix with Y6 to finely adjust phase separation,domain size and molecular arrangement in ternary active layers,which can be confirmed from the characterization on morphology,2 D grazing incidence small and wide-angle X-ray scattering,as well as Raman mapping.In addition,PC71BM may prefer to mix with Y6 to form efficient electron transport channels,which should be conducive to charge transport and collection in the optimized ternary OPVs.This work provides more insight into the underlying reasons of the third component on performance improvement of ternary OPVs,indicating ternary strategy should be an efficient method to optimize active layers for synchronously improving photon harvesting,exciton dissociation and charge transport,while keeping the simple cell fabrication technology.

Au/TS-1 catalyst for propylene epoxidation with H_(2)and O_(2):Effect of surface property and morphology of TS-1 zeolite

The catalytic performances over propylene epoxidation with H_(2)and O_(2)(HOPO process)are significantly affected by the properties(e.g.,surface properties,Ti coordination,morphology)of titanosilicate zeolite.Introducing urea into zeolite synthesis is a simple and convenient method to modify these properties of titanosilicate zeolite.Uncalcined pore-blocked titanium silicalite-1(TS-1,i.e.,TS-1-B)with the lower urea dosage possesses more defective structure and unsaturated coordinated Ti sites verified by 29Si nuclear magnetic resonance(NMR)and X-ray photoelectron spectroscopy(XPS)analysis,which results in a high initial activity and hydrogen efficiency;while the high surface acidity generated by these Ti species leads to a continuous decrease in the activity and the propylene oxide(PO)selectivity during the reaction.As the amount of urea gradually increases,the TS-1-B samples present the reduced surface defects and defective and unsaturated Ti species.Specially,TS-1-B-0.30U presents the weaker PO adsorption on PO-diffusion reflectance infrared Fourier transform spectra(DRIFTS),thus results in the high stable PO formation rate and selectivity over its Au catalyst.Furthermore,a flat-plate-like shape with a shorter thickness of 100 nm along the b-axis direction is observed on the urea-modified TS-1.Compared with the conventional ellipsoidal TS-1 with crystal sizes of 200 and 500 nm,the flat-plate-like TS-1-0.30U displays the less surface defects,unsaturated Ti species,the weaker Lewis acid,which is favorable for the desorption and intracrystalline diffusion of PO,thus reduces the occurrence of side reactions for the improved selectivity and stability.This work may provide a reference for developing titanium-containing materials with high activity and stability over HOPO reaction.

Improving wear and corrosion resistances of Mg_(2)Si/AZ91 composites via tailoring microstructure and intrinsic properties of Mg_(2)Si induced by Sb modification

To achieve simultaneous improvement in wear resistance and corrosion resistance,we propose a novel strategy to successfully develop Mg matrix composites containing blocky primary Mg_(2)Si with small size instead of undesirable dendrite shape and large size.The tribological and corrosion behavior of Mg_(2)Si/AZ91 unmodified and modified with 2.0wt.%Sb was subsequently and systematically investigated.The results show that Sb addition can significantly modify the morphology of primary Mg_(2)Si to blocky polygon with smaller size of 12-25μm,but has less effect onα-Mg grain size.Compared with unmodified composite,Sb modified Mg_(2)Si/AZ91 composite has higher Brinell hardness and nearly unchanged microhardness of the matrix.Sb modified composite exhibits a 26%lower wear loss than unmodified composite suggesting the greatly improved wear resistance.Microstructure analyses indicate that the main wear mechanism of composites is dominated by abrasive wear,and Sb addition can decrease the width and depth of grooves,resulting in a weakened abrasive wear behavior.Additionally microcracks initiation on Sb modified Mg_(2)Si particles can be restricted during the sliding friction process because of higher toughness and blocky polygonal shape induced by Sb doping,which is responsible for the improved wear resistance.Interestingly,Sb modified Mg_(2)Si/AZ91composite also demonstrates a superior corrosion resistance than unmodified composite due to the decrease of calculated corrosion rate from1.57 mm/y to 0.74 mm/y,reduced by 52.8%.Such improvement is closely related to the reduced susceptibility to micro-galvanic corrosion,which is attributed to the reduced volta potential difference of Mg_(2)Si relative to the Mg matrix,from 365 mV to 210 mV.

Strengthening mechanism of different morphologies of nanosized MSH on tribological performance of phosphate/MoS_(2) bonded solid lubricating coatings

Magnesium silicate hydroxides(MSHs)with granular,schistose,and tubular morphologies were separately incorporated to enhance the tribological properties of phosphate/MoS_(2) composite coatings.The nano-schistose MSH demonstrated superior tribological performance due to its effective interactions with the worn surface and frictional synergies with solid lubricants.Incorporation of nano-schistose MSH decreased the friction coefficient of composite coatings by about 34.7%and increased the anti-wear performance of composite coatings by about thirteen times.Nano-schistose MSH facilitated the formation of a friction-induced multi-layer heterogenous slipping structure with layered solid lubricants at the friction interface.Moreover,tribo-chemical reactions between nano-schistose MSH and worn surface promoted the in-situ formation of a cermet supporting film,and this also induced the gradual in-situ formation of a lubrication film on the top of worn surface.Consequently,the contact state between tribo-pairs was timely regulated and the invalidation of the nanocomposite slipping structure was effectively restrained during the friction process.As a result,the service life of the phosphate composite coatings was significantly extended and further abrasion on the worn surface was notably reduced.

Simultaneously Optimizing Molecular Stacking and Phase Separation via Solvent-Solid Hybrid Additives Enables Organic Solar Cells with over 19%Efficiency

Comprehensive Summary Given the crucial role of film morphology in determining the photovoltaic parameters of organic solar cells(OSCs),solvent or solid additives have been widely used to realize fine-tuned film morphological features to further improve the performance of OSCs.However,most high-performance OSCs are processed only using single component additive,either solvent additive or solid additive.Herein,a simple molecular building block,namely thieno[3,4-b]thiophene(TT),was utilized as the solid additive to coordinate with the widely used solvent additive,1-chloronaphthalene(CN),to modulate the film morphology.Systematical investigations revealed that the addition of TT could prevent the excessive aggregation to form a delicate nanoscale phase separation,leading to enhanced charge transport and suppressed charge recombination,as well as superior photovoltaic performance.Consequently,the PM6:Y6 based OSCs with the addition of hybrid additive of CN+TT demonstrated the optimal PCE of 18.52%,with a notable FF of 79.6%.More impressively,the PM6:Y6:PC71BM based ternary OSCs treated with the hybrid additives delivered a remarkable efficiency of 19.05%,which ranks among the best values of Y6-based OSCs reported so far.This work highlights the importance of the hybrid additive strategy in regulating the active layer morphology towards significantly improved performance.

Recent Advances in 0D Ni/Co-based Hollow Electrocatalysts for Electrochemical Water Splitting

Electrochemical water splitting using renewable energy sources has been recognized as a sustainable way to produce hydrogen energy due to the characteristics of low-carbon and no pollution.However,the slow hydrogen/oxygen evolution reactions(HER/OER)seriously hinder the practical application of large-scale water splitting.In this paper,the 0D Ni/Co-based hollow material is discussed in detail because of adjustable morphology,low mass density and abundant active sites,which provides an effective solution for improving the HER/OER reaction kinetics.The synthesis methods of hollow materials,such as hard template,soft template and self-template are introduced.Afterward,catalysts with different structural designs of hollow structures are reviewed,including hollow single-shelled structure,hollow core-shelled structure,hollow double-shelled structure and hollow multi-shelled structure(HoMS)catalysts.Wherein,the research progress of the 0D Ni/Co-based HoMS electrocatalysts in recent years and their prominent performances in water splitting are highlighted.Finally,the challenges and development prospects of designing Ni/Co-based HoMS catalysts in water splitting in the future are discussed.

Regioregular Non-Fused Polymerized Small Molecular Acceptors Enabling Efficient All-Polymer Solar Cells

Comprehensive Summary The regioregularity induced by the isomers of the end-groups has been widely recognized as a key factor that determines the photovoltaic properties of polymerized small molecular acceptors(PSMAs)in all-polymer solar cells(all-PSCs).However,the influence of regioregularity on the photovoltaic properties of non-fused PSMAs has not been explored yet.In this contribution,two regioregular non-fused PSMAs,PFBTz-T-γand PFBTz-T-δ,were synthesized for the first time by using the monomers with isomeric pure end-groups.Compared with PFBTz-T-δ,PFBTz-T-γhas more compact and more ordered packing in solid state,which results in a more red-shifted optical absorption and a higher electron mobility.More remarkably,PFBTz-T-γand PFBTz-T-δexhibited huge difference in photovoltaic performance in all-PSCs,which offered the power conversion efficiencies(PCEs)of 9.72%and 0.52%,respectively.Further studies have unveiled that the higher PCE of PFBTz-T-γis due to more efficient exciton dissociation,higher and more balanced electron/hole mobility,and less charge recombination as a result of favorable morphology of the blend film.This work demonstrates that the development of regioregular non-fused PSMAs by tuning the polymerization sites is an effective strategy for obtaining high-efficiency all-PSCs.