Design principles in MOF-derived electromagnetic wave absorption materials:Review and perspective

At present,metal-organic framework(MOF)-derived nano-micro architectures are actively explored for electromagnetic(EM)wave absorption owing to their flexible composition and structural manipulation that enhance dielectric and magnetic attenuations.However,the basic design principles in MOF-derived microwave absorption materials have not been summarized.This review is devoted to analyzing design principles in MOF-derived microwave absorption materials from the following perspectives:diverse monomers(ligands and ions of MOFs),topologies,chemical states,and physical properties.The derived essential information regarding the EM wave absorption mechanism and the structural-functional dependency is also comprehensively summarized.Finally,a clear insight into the challenges and perspectives of the industrial revolution upgrading in this promising field is proposed.

Revealing the atomic mechanism of diamond–iron interfacial reaction

Diamond,with ultrahigh hardness,high wear resistance,high thermal conductivity,and so forth,has attracted worldwide attention.However,researchers found emergent reactions at the interfaces between diamond and ferrous materials,which significantly affects the performance of diamond-based devices.Herein,combing experiments and theoretical calculations,taking diamond–iron(Fe)interface as a prototype,the counter-diffusion mechanism of Fe/carbon atoms has been established.Surprisingly,it is identified that Fe and diamond first form a coherent interface,and then Fe atoms diffuse into diamond and prefer the carbon vacancies sites.Meanwhile,the relaxed carbon atoms diffuse into the Fe lattice,forming Fe_(3)C.Moreover,graphite is observed at the Fe_(3)C surface when Fe_(3)C is over-saturated by carbon atoms.The present findings are expected to offer new insights into the atomic mechanism for diamondferrous material's interfacial reactions,benefiting diamond-based device applications.

Rational design of diamond through microstructure engineering:From synthesis to applications

Diamond possesses excellent thermal conductivity and tunable bandgap.Currently,the high-pressure,high-temperature,and chemical vapor deposition methods are the most promising strategies for the commercial-scale production of synthetic diamond.Although diamond has been extensively employed in jewelry and cutting/grinding tasks,the realization of its high-end applications through microstructure engineering has long been sought.Herein,we discuss the microstructures encountered in diamond and further concentrate on cutting-edge investigations utilizing electron microscopy techniques to illuminate the transition mechanism between graphite and diamond during the synthesis and device constructions.The impacts of distinct microstructures on the electrical applications of diamond,especially the photoelectrical,electrical,and thermal properties,are elaborated.The recently reported elastic and plastic deformations revealed through in situ microscopy techniques are also summarized.Finally,the limitations,perspectives,and corresponding solutions are proposed.

Microwave-Assisted Confining Growth and Liquid Exfoliation of sp^(3)-Hybrid Carbon Nitride Nano/Micro-Crystals

As one promising carbon-based material,sp^(3)-hybrid carbon nitride has been predicted with various novel physicochemical properties.However,the synthesis of sp^(3)-hybrid carbon nitride is still limited by the nanaoscale,low crystallinity,complex source,and expensive instruments.Herein,we have presented a facile approach to the sp^(3)-hybrid carbon nitride nano/micro-crystals with microwave-assisted confining growth and liquid exfoliation.Actually,the carbon nitride nano/micro-crystals can spontaneously emerge and grow in the microwave-assisted polymerization of citric acid and urea,and the liquid exfoliation can break the bulk disorder polymer to retrieve the highly crystalline carbon nitride nano/micro-crystals.The obtained carbon nitride nano/micro-crystals present superior blue light absorption strength and surprising photoluminescence quantum yields of 57.96% in ethanol and 18.05%in solid state.The experimental characterizations and density functional theory calculations reveal that the interface-trapped localized exciton may contribute to the excellent intrinsic light emission capability of carbon nitride nano/micro-crystals and the interparticle staggered stacking will prevent the aggregation-caused-quenching partially.Finally,the carbon nitride nano/micro-crystals are demonstrated to be potentially useful as the phosphor medium in light-emitting-diode for interrupting blue light-induced eye damage.This work paves new light on the synthesis strategy of sp^(3)-hybrid carbon nitride materials and thus may push forward the development of multiple carbon nitride research.

Synthesis and nitrogen content regulation of diamond in a high-pressure hydrogen-rich environment

The regulating nitrogen content of diamond in a hydrogen-rich high-temperature and high-pressure(HPHT) growth environment was systematically investigated in this work by developing three growth systems,namely, "FeNi+Ti", "FeNi+G_(3)N_(6)H_(6)",and "FeNi+Ti+C_(3)N_(6)H_(6)".Optical microscopy,infrared spectroscopy,and photoluminescence(PL)spectroscopy measurements were conducted to analyze the spectroscopic characteristics of diamonds grown in these three systems.From our analysis,it was demonstrated that the presence of hydrogen in the sp^(3) hybrid C-H does not directly affect the color of the diamond and facilitates the increase of the nitrogen-vacancy(NV) center concentration in a highnitrogen-content diamond.In addition,titanium plays an important role in nitrogen removal,while its impact on hydrogen doping within the diamond lattice is insignificant.Most importantly,by regulating the ratio of nitrogen impurities that coexist in the nitrogen and hydrogen HPHT environment,the production of hydrogenous Ⅱa-type diamond,hydrogenous Ib-type diamond,and hydrogenous high-nitrogen-type diamonds was achieved with a nitrogen content of less than 1 ppm to 1600 ppm.

Performance analysis of single-focus phase singularity based on elliptical reflective annulus quadrangle-element coded spiral zone plates

Optical vortices generated by the conventional vortex lens are usually disturbed by the undesired higher-order foci,which may lead to additional artifacts and thus degrade the contrast sensitivity. In this work, we propose an efficient methodology to combine the merit of elliptical reflective zone plates(ERZPs) and the advantage of spiral zone plates(SZPs) in establishing a specific single optical element, termed elliptical reflective annulus quadrangle-element coded spiral zone plates(ERAQSZPs) to generate single-focus phase singularity. Differing from the abrupt reflectance of the ERZPs, a series of randomly distributed nanometer apertures are adopted to realize the sinusoidal reflectance. Typically, according to our physical design, the ERAQSZPs are fabricated on a bulk substrate;therefore, the new idea can significantly reduce the difficulty in the fabrication process. Based on the Kirchhoff diffraction theory and convolution theorem, the focusing performance of ERAQSZPs is calculated. The results reveal that apart from the capability of generating optical vortices,ERAQSZPs can also integrate the function of focusing, energy selection, higher-order foci elimination, as well as high spectral resolution together. In addition, the focusing properties can be further improved by appropriately adjusting the parameters, such as zone number and the size of the consisted primitives. These findings are expected to direct a new direction toward improving the performance of optical capture, x-ray fluorescence spectra, and forbidden transition.

Strong electron correlation-induced Mott-insulating electrides of Ae_(5)X_(3)(Ae=Ca,Sr,and Ba;X=As and Sb)

The presence of interstitial electrons in electrides endows them with interesting attributes,such as low work function,high carrier concentration,and unique magnetic properties.Thorough knowledge and understanding of electrides are thus of both scientific and technological significance.Here,we employ first-principles calculations to investigate Mott-insulating Ae_(5)X_(3)(Ae=Ca,Sr,and Ba;X=As and Sb)electrides with Mn_(5)Si_(3)-type structure,in which half-filled interstitial electrons serve as ions and are spin-polarized.The Mott-insulating property is induced by strong electron correlation between the nearest interstitial electrons,resulting in spin splitting and a separation between occupied and unoccupied states.The half-filled antiferromagnetic configuration and localization of the interstitial electrons are critical for the Mott-insulating properties of these materials.Compared with that in intermetallic electrides,the orbital hybridization between the half-filled interstitial electrons and the surrounding atoms is weak,leading to highly localized magnetic centers and pronounced correlation effects.Therefore,the Mott-insulating electrides Ae_(5)X_(3)have very large indirect bandgaps(0.30 eV).In addition,high pressure is found to strengthen the strong correlation effects and enlarge the bandgap.The present results provide a deeper understanding of the formation mechanism of Mott-insulating electrides and provide guidance for the search for new strongly correlated electrides.

Phase reconfiguration of heterogeneous CoFeS/CoNiS nanoparticles for superior battery-type supercapacitors

Developing advanced battery-type materials with abundant active sites,high conductivity,versatile morphologies,and hierarchically porous structures is crucial for realizing high-quality hybrid supercapacitors.Herein,heterogeneous FeS@NiS is synthesized by cationic Co doping via surface-structure engineering.The density functional theory(DFT)theoretical calculations are firstly performed to predict the advantages of Co dopant by improving the OH^(−)adsorption properties and adjusting electronic structure,benefiting ions/electron transfer.The dynamic surface evolution is further explored which demonstrates that CoFeS@CoNiS could be quickly reconstructed to Ni(Co)Fe_(2)O_(4)during the charging process,while the unstable structure of the amorphous Ni(Co)Fe_(2)O_(4)results in partial conversion to Ni/Co/FeOOH at high potentials,which contributes to the more reactive active site and good structural stability.Thus,the free-standing electrode reveals excellent electrochemical performance with a superior capacity(335.6 mA h g^(−1),2684 F g^(−1))at 3 A g^(−1).Furthermore,the as-fabricated device shows a quality energy density of 78.1 W h kg^(−1)at a power density of 750 W kg^(−1)and excellent cycle life of 92.1%capacitance retention after 5000 cycles.This work offers a facile strategy to construct versatile morphological structures using electrochemical activation and holds promising applications in energy-related fields.

Dielectric loss enhancement induced by the microstructure of CoFe_(2)O_(4) foam to realize broadband electromagnetic wave absorption

CoFe_(2)O_(4)has been widely used for electromagnetic wave absorption owing to its high Snoek limit,high anisotropy,and suitable saturation magnetization;however,its inherent shortcomings,including low dielectric loss,high density,and magnetic agglomeration,limit its application as an ideal absorbent.This study investigated a microstructure regulation strategy to mitigate the inherent disadvantages of pristine CoFe_(2)O_(4)synthesized via a sol–gel auto-combustion method.A series of CoFe_(2)O_(4)foams(S0.5,S1.0,and S1.5,corresponding to foams with citric acid(CA)-to-Fe(NO_(3))_(3)·9H_(2)O molar ratios of 0.5,1.0,and 1.5,respectively)with two-dimensional(2D)curved surfaces were obtained through the adjustment of CA-to-Fe^(3+)ratio,and the electromagnetic parameters were adjusted through morphology regulation.Owing to the appropriate impedance matching and conductance loss provided by moderate complex permittivity,the effective absorption bandwidth(EAB)of S0.5 was as high as 7.3 GHz,exceeding those of most CoFe_(2)O_(4)-based absorbents.Moreover,the EAB of S1.5 reached 5.0 GHz(8.9–13.9 GHz),covering most of the X band,owing to the intense polarization provided by lattice defects and the heterogeneous interface.The three-dimensional(3D)foam structure circumvented the high density and magnetic agglomeration issues of CoFe_(2)O_(4)nanoparticles,and the good conductivity of 2D curved surfaces could effectively elevate the complex permittivity to ameliorate the dielectric loss of pure CoFe_(2)O_(4).This study provides a novel idea for the theoretical design and practical production of lightweight and broadband pure ferrites.

Diamond growth in a high temperature and high pressure Fe–Ni–C–Si system:Effect of synthesis pressure

Pressure is one of the necessary conditions for diamond growth.Exploring the influence of pressure on growth changes in silicon-doped diamonds is of great value for the production of high-quality diamonds.This work reports the morphology,impurity content and crystal quality characteristics of silicon-doped diamond crystals synthesized under different pressures.Fourier transform infrared spectroscopy shows that with the increase of pressure,the nitrogen content in the C-center inside the diamond crystal decreases.X-ray photoelectron spectroscopy test results show the presence of silicon in the diamond crystals synthesized by adding silicon powder.Raman spectroscopy data shows that the increase in pressure in the Fe-Ni-C-Si system shifts the Raman peak of diamonds from 1331.18 cm^(-1)to 1331.25 cm^(-1),resulting in a decrease in internal stress in the crystal.The half-peak width decreased from 5.41 cm^(-1)to 5.26 cm^(-1),and the crystallinity of the silicon-doped diamond crystals improved,resulting in improved quality.This work provides valuable data that can provide a reference for the synthesis of high-quality silicon-doped diamonds.

Editorial for special issue on electromagnetic wave absorbing materials

With the rapid development of information technology and electronics industry,stealth warplanes,radar stealth,electronic countermeasures,microwave communications,and other equipment have played an increasingly important role in military defense.Therefore,the design and development of new electromagnetic wave(EMW)absorbing materials with high performance and environmental applicability that can be widely used in the microwave field has become a key issue and a major strategic challenge that needs to be urgently addressed in the modernization and upgrading of major advanced military equipment.However,how to effectively address the growing electromagnetic pollution has been an important issue that has plagued researchers in the field of EMW absorption for many years.

Achieving Tunable Cold/Warm White‑Light Emission in a Single Perovskite Material with Near‑Unity Photoluminescence Quantum Yield

Single materials that exhibit efficient and stable white-light emission are highly desirable for lighting applications.This paper reports a novel zero-dimensional perovskite,Rb_(4)CdCl_(6):Sn^(2+),Mn^(2+),which demonstrates exceptional white-light properties including adjustable correlated color temperature,high color rendering index of up to 85,and near-unity photoluminescence quantum yield of 99%.Using a co-doping strategy involving Sn^(2+)and Mn^(2+),cyan-orange dual-band emission with complementary spectral ranges is activated by the self-trapped excitons and d-d transitions of the Sn^(2+)and Mn^(2+)centers in the Rb_(4)CdCl_(6)host,respectively.Intriguingly,although Mn^(2+)ions doped in Rb_(4)CdCl_(6)are difficult to excite,efficient Mn^(2+)emission can be realized through an ultra-high-efficient energy transfer between Sn^(2+)and Mn^(2+)via the formation of adjacent exchange-coupled Sn–Mn pairs.Benefiting from this efficient Dexter energy transfer process,the dual emission shares the same optimal excitation wavelengths of the Sn^(2+)centers and suppresses the non-radiative vibration relaxation significantly.Moreover,the relative intensities of the dual-emission components can be modulated flexibly by adjusting the fraction of the Sn^(2+)ions to the Sn–Mn pairs.This co-doping approach involving short-range energy transfer represents a promising avenue for achieving high-quality white light within a single material.

Tuning Lithiophilicity and Stability of 3D Conductive Scaffold via Covalent Ag-S Bond for High-Performance Lithium Metal Anode

Li metal anode holds great promise to realize high-energy battery systems.However,the safety issue and limited lifetime caused by the uncontrollable growth of Li dendrites hinder its commercial application.Herein,an interlayer-bridged 3D lithiophilic rGO-Ag-S-CNT composite is proposed to guide uniform and stable Li plating/stripping.The 3D lithiophilic rGO-Ag-S-CNT host is fabricated by incorporating Ag-modified reduced graphene oxide(rGO)with S-doped carbon nanotube(CNT),where the rGO and CNT are closely connected via robust Ag-S covalent bond.This strong Ag-S bond could enhance the structural stability and electrical connection between rGO and CNT,significantly improving the electrochemical kinetics and uniformity of current distribution.Moreover,density functional theory calculation indicates that the introduction of Ag-S bond could further boost the binding energy between Ag and Li,which promotes homogeneous Li nucleation and growth.Consequently,the rGO-Ag-S-CNT-based anode achieves a lower overpotential(7.3 mV at 0.5 mA cm^(−2)),higher Coulombic efficiency(98.1%at 0.5 mA cm^(−2)),and superior long cycling performance(over 500 cycles at 2 mA cm−2)as compared with the rGO-Ag-CNT-and rGO-CNT-based anodes.This work provides a universal avenue and guidance to build a robust Li metal host via constructing a strong covalent bond,effectively suppressing the Li dendrites growth to prompt the development of Li metal battery.

Hybrid 2D/3D Graphitic Carbon Nitride-Based High-Temperature Position-Sensitive Detector

Ultraviolet position-sensitive detectors(PSDs)are expected to undergo harsh environments,such as high temperatures,for a wide variety of applications in military,civilian,and aerospace.However,no report on relevant PSDs operating at high temperatures can be found up to now.Herein,we design a new 2D/3D graphitic carbon nitride(g-C_(3)N_(4))/gallium nitride(GaN)hybrid heterojunction to construct the ultraviolet high-temperature-resistant PSD.The g-C_(3)N_(4)/GaN PSD exhibits a high position sensitivity of 355 mV mm^(-1),a rise/fall response time of 1.7/2.3 ms,and a nonlinearity of 0.5%at room temperature.The ultralow formation energy of-0.917 eV atom^(-1)has been obtained via the thermodynamic phase stability calculations,which endows g-C_(3)N_(4)with robust stability against heat.By merits of the strong built-in electric field of the 2D/3D hybrid heterojunction and robust thermo-stability of g-C_(3)N_(4),the g-C_(3)N_(4)/GaN PSD delivers an excellent position sensitivity and angle detection nonlinearity of 315 mV mm^(-1)and 1.4%,respectively,with high repeatability at a high temperature up to 700 K,outperforming most of the other counterparts and even commercial silicon-based devices.This work unveils the high-temperature PSD,and pioneers a new path to constructing g-C_(3)N_(4)-based harsh-environment-tolerant optoelectronic devices.

Lightweight Dual‑Functional Segregated Nanocomposite Foams for Integrated Infrared Stealth and Absorption‑Dominant Electromagnetic Interference Shielding

Lightweight infrared stealth and absorption-dominant electromagnetic interference(EMI)shielding materials are highly desirable in areas of aerospace,weapons,military and wearable electronics.Herein,lightweight and high-efficiency dual-functional segregated nanocomposite foams with microcellular structures are developed for integrated infrared stealth and absorption-dominant EMI shielding via the efficient and scalable supercritical CO_(2)(SC-CO_(2))foaming combined with hydrogen bonding assembly and compression molding strategy.The obtained lightweight segregated nanocomposite foams exhibit superior infrared stealth performances benefitting from the synergistic effect of highly effective thermal insulation and low infrared emissivity,and outstanding absorption-dominant EMI shielding performances attributed to the synchronous construction of microcellular structures and segregated structures.Particularly,the segregated nanocomposite foams present a large radiation temperature reduction of 70.2℃ at the object temperature of 100℃,and a significantly improved EM wave absorptivity/reflectivity(A/R)ratio of 2.15 at an ultralow Ti_(3)C_(2)T_(x) content of 1.7 vol%.Moreover,the segregated nanocomposite foams exhibit outstanding working reliability and stability upon dynamic compression cycles.The results demonstrate that the lightweight and high-efficiency dual-functional segregated nanocomposite foams have excellent potentials for infrared stealth and absorption-dominant EMI shielding applications in aerospace,weapons,military and wearable electronics.

Defects‑Rich Heterostructures Trigger Strong Polarization Coupling in Sulfides/Carbon Composites with Robust Electromagnetic Wave Absorption

Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,however,constrain their delicate constructions.Herein,an innovative alternative is proposed:carrageenan-assistant cations-regulated(CACR)strategy,which induces a series of sulfides nanoparticles rooted in situ on the surface of carbon matrix.This unique configuration originates from strategic vacancy formation energy of sulfides and strong sulfides-carbon support interaction,benefiting the delicate construction of defects-rich heterostructures in M_(x)S_(y)/carbon composites(M-CAs).Impressively,these generated sulfur vacancies are firstly found to strengthen electron accumulation/consumption ability at heterointerfaces and,simultaneously,induct local asymmetry of electronic structure to evoke large dipole moment,ultimately leading to polarization coupling,i.e.,defect-type interfacial polarization.Such“Janus effect”(Janus effect means versatility,as in the Greek two-headed Janus)of interfacial sulfur vacancies is intuitively confirmed by both theoretical and experimental investigations for the first time.Consequently,the sulfur vacancies-rich heterostructured Co/Ni-CAs displays broad absorption bandwidth of 6.76 GHz at only 1.8 mm,compared to sulfur vacancies-free CAs without any dielectric response.Harnessing defects-rich heterostructures,this one-pot CACR strategy may steer the design and development of advanced nanomaterials,boosting functionality across diverse application domains beyond electromagnetic response.

Influences of complex modification of P and RE on microstructure and mechanical properties of hypereutectic Al-20Si alloy

P and RE complex modification of hypereutectic Al-Si alloys was conducted. The influences of P, RE content on the microstructure and mechanical properties of alloys were investigated. The complex modifications of P and RE make the coarse block primary silicon obviously refined and the large needle eutectic silicon modified to the fine fibrous or lamella ones. P mainly refines the primary silicon, but excess P is unfavorable to the refinement of primary silicon. RE can well refine the primary and eutectic silicon, but its modification effect on the eutectic silicon is more obvious. P can repress the modification of RE on the eutectic silicon. The alloys with the additions of 0.08% P and 0.60% RE have the optimal microstructure and the highest mechanical properties. Compared with the unmodified alloy, the primary silicon of alloys can be refined from 66.4 μm to 23.3 μm and the eutectic silicon can be refined from 8.3 μm to 5.2 μm. The tensile strength is improved from 256 MPa to 306 MPa and the elongation is improved from 0.35% to 0.48%.

Influence of trace Ca addition on texture and stretch formability of AM50 magnesium alloy sheet

The AM50,AM50-0.1 Ca,AM50-0.3 Ca and AM50-0.5 Ca(wt.%) alloys were hot-rolled and their mechanical properties were determined for the purpose of investigating the effect of trace Ca addition on the texture and stretch formability of AM50 alloy.The results show that the addition of trace Ca can effectively modify the basal texture,which is characterized by the split of basal poles deviated from the normal direction(ND) after the hot rolling,while a broad spread of the basal planes toward the transverse direction(TD) after the annealing.Such change of the basal texture is related to the prior formation of massive compression twins and the decrease of the c/a ratio.Erichsen value increases from 2.25 to 4.21 mm with the increase of Ca content.The enhancement of stretch formability is ascribed to the weakened basal texture,which results in the increase of n-value and the decrease of r-value.

MOF-derived multifunctional filler reinforced polymer electrolyte for solid-state lithium batteries

Solid-state lithium batteries(SSLBs) have attracted great interest from researchers due to their inherent high energy density and high safety performance.In order to develop SSLBs,the following two key problems should be solved:(1) Improving the lithium ion conductivity of solid electrolyte at room temperature;and(2) improving the interface between the electrode and the electrolyte.Herein,we propose a new multifunctional filler for reinforcing polymer electrolytes.The composite solid electrolytes(CSEs)mainly contain a MOF-derived Co-doped hollow porous carbon nanocage,which absorbs Li~+ containing ionic liquid(Li-ILs@HPCN),polyethylene oxide(PEO) and lithium bis(trifluoromethanesulfonyl)imide.By optimizing the composition of the CSEs,the CSEs membrane with high ionic conductivity(1.91×10^(-4) S cm^(-1) at 30℃),wide electrochemical stability(5.2 V) and high mobility of lithium ion(0.5) was obtained.Even at a current density of 0.2 mA cm^(-2),the PILH electrolyte possesses excellent interfacial stability against Li metal in Li symmetrical batteries exceeds 1600 h.Finally,the SSLBs(LFP/PILH/Li) showed excellent cycle stability,and the capacity was maintained at 152.9 and140.0 mA h g^(-1) after 150 cycles at a current density of 0.2 C and 0.5 C.This work proposes a completely new strategy for building high-performance SSLBs.

Oxygen adsorption/desorption behavior of YBaCo4O7+δ and its application to oxygen removal from nitrogen

A new medium-temperature (200-400 °C) adsorbent material for oxygen removal and air separation, YBaCo4O7+δ, was prepared by the solid-state reaction method. This new adsorbent could adsorb a large quantity of oxygen in the temperature range of 200-370 °C. Adsorbed oxygen could be released by raising temperature over 400 °C or by switching the atmosphere from oxygen to nitrogen. This oxygen adsorption and desorption process had good reproducibility. Taking advantage of this unique oxygen intake/release behavior, a nitrogen purification process was investigated. The results showed that YBaCo4O7+δ material was a promising candidate for the oxygen sorption process and could be used to produce high-purity nitrogen or to remove trace oxygen from other gases.