Photophysics of metal-organic frameworks:A brief overview

Metal-organic frameworks(MOFs),which are self-assembled porous coordination materials,have garnered considerable attention in the fields of optoelectronics,photovoltaic,photochemistry,and photocatalysis due to their diverse structures and excellent tunability.However,the performance of MOF-based optoelectronic applications currently falls short of the industry benchmark.To enhance the performance of MOF materials,it is imperative to undertake comprehensive investigations aimed at gaining a deeper understanding of photophysics and sequentially optimizing properties related to photocarrier transport,recombination,interaction,and transfer.By utilizing femtosecond laser pulses to excite MOFs,time-resolved optical spectroscopy offers a means to observe and characterize these ultrafast microscopic processes.This approach adds the time coordinate as a novel dimension for comprehending the interaction between light and MOFs.Accordingly,this review provides a comprehensive overview of the recent advancements in the photophysics of MOFs and additionally outlines potential avenues for exploring the time domain in the investigation of MOFs.

In situ observation of the phase transformation kinetics of bismuth during shock release

A time-resolved x-ray diffraction technique is employed to monitor the structural transformation of laser-shocked bismuth.Results reveal a retarded transformation from the shock-induced Bi-Ⅴphase to a metastable Bi-Ⅳphase during the shock release,instead of the thermodynamically stable Bi-Ⅲphase.The emergence of the metastable Bi-Ⅳphase is understood by the competitive interplay between two transformation pathways towards the Bi-Ⅳand Bi-Ⅲ,respectively.The former is more rapid than the latter because the Bi-Ⅴto B-Ⅳtransformation is driven by interaction between the closest atoms while the Bi-Ⅴto B-Ⅲtransformation requires interaction between the second-closest atoms.The nucleation time for the Bi-Ⅴto Bi-Ⅳtransformation is determined to be 5.1±0.9 ns according to a classical nucleation model.This observation demonstrates the importance of the formation of the transient metastable phases,which can change the phase transformation pathway in a dynamic process.

Oxidation behavior of Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2)C-M_(x)C(M=Ti,Zr,Hf,Nb,Ta) composite ceramic at high temperature

Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2)C-M_(t)C composite ceramic was prepared by hot press sintering,with the Ti_(0.2)Zr_(0.2)Hf_(0.2)Nb_(0.2)Ta_(0.2)C high-entropy carbide as the main phase.Secondary phase M_(x)C(M=Ti,Zr,Hf,Nb,Ta) was found to be distributed relatively uniform in the composite ceramic.The oxidation behavior of the ceramic was examined after exposure to 923 K and 1173 K.Morphology of the surface and cross sections of all oxidation samples were observed.The characteristics of the oxidation behavior of the high-entropy carbide and the secondary phase M_(x)C were compared and analyzed.The secondary phases(such as Ti-rich carbide or Hf-rich carbide) in the material were seriously oxidized at 923 K and 1173 K,which reflects the superior oxidation performance of the high-entropy carbide.The nano high-entropy oxides with Ti,Zr,Hf,Nb,Ta,and O elements were discovered by oxidation of the composite ceramic.This research will help deepen the understanding of the oxidation mechanism of high-entropy carbide and composite ceramic.

Microscale insights into the influence of grinding media on spodumene micro-flotation using mixed anionic/cationic collectors

Here,the influence of grinding media with different shapes on the flotation performance of spodumene and its potential mechanism from microscale insights was investigated using a single mineral flotation experiment,X-ray diffraction(XRD)test,scanning electron microscopy combined with energy dispersive spectrometry(SEM-EDS),atomic force microscope(AFM)and X-ray photoelectron spectroscopy(XPS).The flotation data indicated that under anionic/cationic(sodium oleate(NaOL)/DDA)collectors system,the rod milled spodumene has a higher floatability than ball milled ones.XRD results confirmed that rod medium makes spodumene exposed more{110}and{100}planes,while ball medium makes spodumene exposed more{010}planes.The typical anisotropic surface of spodumene makes the surface of rod milled spodumene possess more Al sites,further confirmed by SEM-EDS and XPS results.Additionally,it was found that the rod milled spodumene presents a larger value of elongation and flatness,which are parameters closely related to bubble adhesion.AFM analysis indicated that rod milled products have a rougher surface,while ball milled products have a smoother surface.Consequently,the rod medium enhanced the adsorption of NaOL/DDA on the spodumene surfaces.This work provides theoretical guidance for optimizing the separation of spodumene from the perspective of grinding.

An in situ ATR-FTIR study of mixed collectors BHA/DDA adsorption in ilmenite-titanaugite flotation system

This paper researched the enhanced flotation separation performance of ilmenite and titanaugite using the mixed collector benzhydroxamic acid/dodecylamine(BHA/DDA).The interface assembly mechanism was mainly investigated through in situ attenuated total reflectance Fourier transform infrared(ATRFTIR)spectroscopy combined with the two-dimensional correlation spectroscopy(2D-COS)and X-ray photoelectron spectroscopy(XPS).It has been found that BHA/DDA mixed collectors successfully separate ilmenite from titanaugite at a molar ratio of 8:1.Zeta potential experiments suggested that,in the presence of mixed collector system,the BHA-DDA complex adsorbed on the ilmenite surface via the chemically adsorbed BHA and the electrostatically adsorbed DDA,however,the complex adsorbed on the surface of titanaugite unstably.According to in situ ATR-FTIR combined with 2D-COS and XPS results,the interface assembly mechanism of BHA/DDA is summarized as:the function group of BHA molecules first binds to the metal sites on minerals to form bidentate ligand,then DDA co-adsorbed with BHA on the surface of minerals through hydrogen bonding.DDA may change the adsorption modes of some BHA on the ilmenite surface from four-membered ring to five-membered ring,while the modes on the titanaugite surface is true opposite.Finally,recommended adsorption configurations of the BHA/DDA complex on the two mineral surfaces are proposed.

锂辉石尾矿制备陶瓷材料的烧结行为及其力学性能

本文以锂辉石浮选尾矿为主要原料,低熔点玻璃粉(LPG)为高温粘结材料,通过湿法注模成型,常压烧结制备陶瓷材料。通过正交试验研究了烧结温度和LPG质量分数对陶瓷材料抗折强度和抗压强度的影响。结果表明,当LPG质量比不低于20 wt%,烧结温度不低于550℃时,尾矿颗粒间相互粘结紧密,制备出了力学性能优异的陶瓷材料(最大抗折强度=19.55 MPa,最大抗压强度=42.25 MPa,平均显气孔率24.52%,体积密度1.66 g/cm^(3),吸水率14.79%)。采用XRF、XRD、光学显微镜、SEM、TGA-DSC和FT-IR等对陶瓷材料低温烧结机理进行了测试分析。结果表明,高温下液相的生成使得颗粒间相互粘结可能为陶瓷材料力学性能提高的主要原因。

Formation of nano-twinned 3C-SiC grains in Fe-implanted 6H-SiC after 1500-℃annealing

A nano-twinned microstructure was found in amorphous SiC after high-temperature annealing.Grazing incidence x-ray diffraction,high-resolution transmission electron microscopy,and electron diffraction were performed to characterize the microstructure and phase transition in the recrystallization layer.After 1500℃or 2-h annealing,3C-SiC grains and numerous stacking faults on the{111}planes were visible.Some 3C-SiC grains have nano-twinned structure with{011}planes.Between the nano-twinned 3C-SiC grains,there is a stacking fault,indicating that the formation mechanisms of the nano-twinned structure are related to the disorder of Si atoms.The increase in the twin thickness with increasing annealing temperature demonstrates that the nano-twinned structure can sink for lattice defects,in order to improve the radiation tolerance of SiC.

Effect of Synthesis Process on CuO Segregation and Dielectric Properties of CaCu3Ti4O12 Ceramic

The CaCu3Ti4O12(CCTO) ceramic was prepared through conventional solid-state method. The effects of synthesis process(synthesis temperature and synthesis time) of powder on ceramic microstructures, CuO segregation and electrical properties were investigated. The phase composition was determined by X-ray diffraction and the microstructure was examined by SEM. The dielectric constant, dielectric loss, and resistance of the ceramic were also determined by a precision impedance tester. The results show that, as the synthesis temperature increases, the CCTO ceramic grain size decreases and the stoichiometric ratio of Cu/Ca at the grain boundary increases, the dielectric constant increases and the dielectric loss decreases(40 < f < 10 kHz). In addition, when the synthesis time is shorter than 12 h, the Cu/Ca ratio of CCTO decreases and the dielectric constant increases with time increase. However, when the synthesis time exceeds 12 h, this trend is just the opposite. It is further proved that Cu at the grain boundary is not conducive to the dielectric constant of CCTO.

Surface chemical disorder and lattice strain of GaN implanted by 3-MeV Fe^(10+)ions

Chemical disorder on the surface and lattice strain in GaN implanted by Fe^(10+)ions are investigated.In this study,3-MeV Fe^(10+)ions fluence ranges from 1×10^(13)ions/cm^(2)to 5×10^(15)ions/cm^(2)at room temperature.X-ray photoelectron spectroscopy,high-resolution x-ray diffraction,and high-resolution transmission electron microscopy were used to characterize lattice disorder.The transition of Ga-N bonds to oxynitride bonding is caused by ion sputtering.The change of tensile strain out-of-plane with fluence was measured.Lattice disorder due to the formation of stacking faults prefers to occur on the basal plane.

Comparison of cavities and extended defects formed in helium-implanted 6H-SiC at room temperature and 750 ℃

The formation of cavities in silicon carbide is vitally useful to“smart-cut”and metal gettering in semiconductor industry.In this study,cavities and extended defects formed in helium(He)ions implanted 6H-SiC at room temperature(RT)and 750℃ followed by annealing at 1500℃are investigated by a combination of transmission electron microscopy and high-resolution electron microscopy.The observed cavities and extended defects are related to the implantation temperature.Heterogeneously distributed cavities and extended defects are observed in the helium-implanted 6H-SiC at RT,while homogeneously distributed cavities and extended defects are formed after He-implanted 6H-SiC at 750℃.The possible reasons are discussed.

Effect of helium concentration on irradiation damage of Fe-ion irradiated SIMP steel at 300℃and 450℃

SIMP steel is newly developed fully martensitic steel for lead-cooled fast reactors and accelerator-driven systems.It is important to evaluate its radiation resistance via high flux neutron irradiation,where dense He atoms can be formed via(n,α)transmutation reaction.Co-irradiation with Fe and He ions,instead of neutron,was performed.Specimens were irradiated with 6.4-MeV Fe ions to the damage dose of 5 dpa at a depth of 600 nm.Three different helium injection ratios of 60-appm He/dpa(dpa:displacements per atom),200-appm He/dpa and 600-appm He/dpa at a depth of 600 nm,were performed.Two different irradiation temperatures of 300℃and 450℃were carried out.The effect of helium concentration on the microstructure of Fe-irradiated SIMP steel was investigated.Microstructural damage was observed using transmission electron microscopy.The formed dislocation loops and bubbles depended on the helium injection ratio and irradiation temperature.Lots of dislocation loops and helium bubbles were homogeneously distributed at 300℃,but not at 450℃.The causes of observed effects are discussed.

Comparison of helium bubble formation in F82H, ODS, SIMP and T91 steels irradiated by Fe and He ions simultaneously

Ferritic-martensitic steels and ODS steels are attractive candidates for structural materials in advanced nuclear-power systems due to their good swelling resistance. Four kinds of steels, F82 H, 15 Cr-ODS, SIMP and T91, are investigated in this study. We take 6.4 Me V Fe3+ ions and energy-degraded 1.0 Me V He+ ions in the irradiation of these materials to 5 dpa and 60 appm He/dpa, 200 appm He/dpa and 600 appm He/dpa at 300℃ and 450℃, respectively. The bubble formation and distribution are investigated by transmission electron microscopy(TEM). Formation and distribution of the bubbles in the four investigated steels are compared. The influence of irradiation temperature and helium injection ratio on bubble formation is discussed. It is found that there appears to be homogenously distributed bubbles at 300℃ irradiation while heterogeneously distributed bubbles at 450℃ irradiation.

Optical spectroscopy study of damage evolution in 6H-SiC by H_(2)^(+)implantation

Lattice defects induced by ion implantation into SiC have been widely investigated in the decades by various techniques.One of the non-destructive techniques suitable to study the lattice defects in SiC is the optical characterization.In this work,confocal Raman scattering spectroscopy and photoluminescence spectrum have been used to study the effects of 134-keV H_(2)^(+)implantation and thermal treatment in the microstructure of 6H-SiC single crystal.The radiation-induced changes in the microstructure were assessed by integrating Raman-scattering peaks intensity and considering the asymmetry of Raman-scattering peaks.The integrated intensities of Raman scattering spectroscopy and photoluminescence spectrum decrease with increasing the fluence.The recovery of the optical intensities depends on the combination of the implantation temperature and the annealing temperature with the thermal treatment from 700℃to 1100℃.The different characterizations of Raman scattering spectroscopy and photoluminescence spectrum are compared and discussed in this study.

Effects of Helium Implantation and Subsequent Electron Irradiation on Microstructures of Fe-11 wt.% Cr Model Alloy

Helium effects on dislocation and cavity formation of Fe-11 wt.% Cr model alloy are investigated. Single-beam(electron) and dual-beam(He^+/e^-) irradiations are performed at 350℃ and 400℃ using an ultra-high voltage electron microscope combined with ion accelerators. In-situ observation shows that the growth rate of dislocation loops is reduced in the helium pre-injected specimen. The mean size of cavities decreased in the helium preinjected specimen. The possible mechanisms are discussed.

Atomic Mixing Induced by Ion Irradiation of V/Cu Multilayers

Bulk Cu/V multilayers simultaneously possess high strength and excellent radiation resistance thanks to their high density of interfaces.Irradiation-induced atomic mixing of Cu/V multilayers has been less investigated.Here,we investigate the ion irradiation of bulk Cu/V multilayers exposed to H2^+ or He^+ ions at 350℃.The microstructure and elemental distribution are investigated by transmission electron microscopy and energy dispersive x-ray spectroscopy.Facetted bubbles and atomic mixing are observed after ion irradiation.The possible mechanisms of irradiation-induced atomic mixing are discussed.

Comparison of Cavities Formed in Single Crystalline and Polycrystalline α-SiC after H Implantation

Cavities and extended defects formed in single crystalline and polycrystalline α-SiC implanted with H+ions are compared.The samples are investigated by cross-sectional transmission electron microscopy.H2 bubbles are formed during H implantation and H2 molecules escape the sample to form cavities during thermal annealing at 1100℃.Microcracks and the extended defects prefer to nucleate in single crystalline α-SiC,but not polycrystalline α-Si C.Grain boundaries can account for the experimental results.The formation of cavities on grain boundaries is investigated.

Metal−Organic Framework-Based Ultrafast Logic Gates for High-Security Optical Encryption

Optical logic gates call for materials with giant optical nonlinearity to break the current performance bottleneck.Metal–organic frameworks(MOFs)provide an intriguing route to achieve superior optical nonlinearity benefitting from structural diversity and design flexibility.However,the potential of MOFs for optoelectronics has been largely overlooked and their applications in optical logic have not been exploited.Here,through temporally manipulating the nonlinear optical absorption process in porphyrin-based MOFs,we have successfully developed AND and XOR logic gates with an ultrafast speed approaching 1 THz and an on–off ratio above 90%.On this basis,all-optical information encryption is further demonstrated using transmittance as primary codes,which shows vast prospects in avoiding the disclosure of security information.To the best of our knowledge,this is the first exploration of MOFs for applications in ultrafast optical logic devices and information encryption.

Surface chemistry considerations of gangue dissolved species in the bastnaesite flotation system

Inefficient flotation of bastnaesite remains a challenge in the production of rare earth elements.This study aimed to investigate the dissolution and adsorption behaviour of species that are commonly released into bastnaesite flotation pulp from Ca/Ba-bearing gangue minerals.The influence and corresponding mechanisms on the bastnaesite mineral surface and collectors,namely sodium oleate(NaOL),were evaluated experimentally based on micro-flotation,zeta potentials,in situ attenuated total reflection Fourier transform infrared spectroscopy(ATRFTIR),and X-Ray photoelectron spectroscopy(XPS)analyses.The flotation recovery of bastnaesite significantly decreased from ~95% to ~25%,~15%,~80%,~25% when exposed to calcite,fluorite,barite,and mixed dissolved species,respectively.The zeta potential of bastnaesite was pH sensitive,indicating that H^(+) and OH^(−)determine the surface potential of bastnaesite.Solution chemistry analyses revealed that the presence of the dissolved species differed at various pH values.In situ ATR-FTIR demonstrated the different effects of the dissolved species from calcite,fluorite,and barite on collector adsorption.The former two dissolved species mainly depressed the chemisorption of the NaOL monomers(RCOO^(-)),whereas calcite also affected the physical adsorption of the oleic acid molecular dimer(RCOOH·RCOO^(-)).Moreover,the barite dissolved species only affected the physical adsorption of the NaOL species.The results of XPS analysis revealed that dissolved species from these three gangues could pre-adsorbed onto bastnaesite and affected the interaction with the collector.Density functional theory calculations were employed to provide further theoretical insights into the interactions between the dissolved species from calcite,fluorite,and barite and NaOL.

On the helium bubble swelling in nano-oxide dispersion-strengthened steels

The development of structural materials resistant to harsh radiation environments requires an in-depth understanding of the early stage of the aging processes.In radiation environments with high transmutation helium production rates such as in fusion and spallation applications,even materials with otherwise acceptable radiation stability may suffer from radiation embrittlement related to helium bubble formation.While theoretical modeling of helium-assisted cavity nucleation in pure metals and simple alloys provides some useful guidelines at the atomic scale level,these,however,do not overlap with the size resolution of available experimental techniques.In this study,we employed slow positron beam spectroscopy to characterize the nucleation and growth of nano-scale helium bubbles in martensitic steels strengthened by thermodynamically stable nano-oxide dispersoids.In combination with transmission electron microscopy,we experimentally characterized the evolution of helium bubbles from small clusters of radiation-induced vacancies to large cavities well resolvable by TEM.Superior radiation resistance of oxide-dispersion strengthened steels dominates only in the early stages of bubble evolution,where positron lifetime measurements provide a missing piece of the microstructural puzzle conventionally constructed by TEM.

Photoluminescence and Raman Spectroscopy Study on Color Centers of Helium Ion-Implanted 4H-SiC

Color centers in silicon carbide(SiC)are promising candidates for quantum technologies.However,the richness of the polytype and defect configuration of SiC makes the accurate control of the types and position of defects in SiC still challenging.In this study,helium ion-implanted 4H-SiC was characterized by atomic force microscopy(AFM),confocal photoluminescence(PL),and confocal Raman spectroscopy at room temperature.PL signals of silicon vacancy were found and analyzed using 638-nm and 785-nm laser excitation by means of depth profiling and SWIFT mapping.Lattice defects(C-C bond)were detected by continuous laser excitation at 532 nm and 638 nm,respectively.PL/Raman depth profiling was helpful in revealing the three-dimensional distribution of produced defects.Differences in the depth profiling results and SRIM simulation results were explained by considering the depth resolution of the confocal measurement setup,helium bubbles,as well as swelling.