KOH-assisted aqueous synthesis of bimetallic metal-organic frameworks and their derived selenide composites for efficient lithium storage

To solve low efficiency,environmental pollution,and toxicity for synthesizing zeolitic imidazolate frameworks(ZIFs)in organic solvents,a KOH-assisted aqueous strategy is proposed to synthesize bimetallic ZIFs polyhedrons,which are used as precursors to prepare bimetallic selenide and N-doped carbon(NC)composites.Among them,Fe–Co–Se/NC retains the three-dimensional(3D)polyhedrons with mesoporous structure,and Fe–Co–Se nanoparticles are uniform in size and evenly distributed.When assessed as anode material for lithium-ion batteries,Fe–Co–Se/NC achieves an excellent initial specific capacity of 1165.9 m Ah·g^(-1)at 1.0 A·g^(-1),and the reversible capacity of Fe–Co–Se/NC anode is 1247.4 m Ah·g^(-1)after 550 cycles.It is attributed to that the uniform composite of bimetallic selenides and N-doped carbon can effectively tune redox active sites,the stable 3D structure of Fe–Co–Se/NCs guarantees the structural stability and wettability of the electrolyte,and the uniform distribution of Fe–Co–S nanoparticles in size esuppresses the volume expansion and accelerates the electrochemical reaction kinetics.

Effect of thickness of antimony selenide film on its photoelectric properties and microstructure

Antimony selenide(Sb2Se3) films are widely used in phase change memory and solar cells due to their stable switching effect and excellent photovoltaic properties. These properties of the films are affected by the film thickness. A method combining the advantages of Levenberg–Marquardt method and spectral fitting method(LM–SFM) is presented to study the dependence of refractive index(RI), absorption coefficient, optical band gap, Wemple–Di Domenico parameters, dielectric constant and optical electronegativity of the Sb2Se3films on their thickness. The results show that the RI and absorption coefficient of the Sb2Se3films increase with the increase of film thickness, while the optical band gap decreases with the increase of film thickness. Finally, the reasons why the optical and electrical properties of the film change with its thickness are explained by x-ray diffractometer(XRD), energy dispersive x-ray spectrometer(EDS), Mott–Davis state density model and Raman microstructure analysis.

A one-pot stereoselective synthesis of 1,4-dienyl selenides by hydrostannylation-Stille tandem reaction of acetylenic selenides with Bu_3SnH and allylic bromides

1,4-Dienyl selenides can be stereoselectively synthesized in one pot under mild conditions in good yields by the palladiumcatalyzed hydrostannylation of acetylenic selenides, followed by Stille coupling with allylic bromides.

Reduction of Diaryldiselenides by System of Cp_2TiCl_2/Bu^iMgBr/THF and Its Application in Synthesis of Unsymmetrical Diaryl Selenides

Reduction of diaryldiselenides by the system of Cp2TiCl2/Bu'MgBr/THF gave the nucleophilic arylselenium complex. They reacted with diaryl iodonium salts to afford unsymmetrical diaryl selenides in high yields.

A convenient and stereoselective synthesis of (Z)-allyl selenides via Sm/TMSCl system-promoted coupling of Baylis-Hillman adducts with diselenides

A simple and convenient procedure for stercoselective synthesis of （Z）-allyl selenides has been developed by a one-pot reaction of diselenides with Baylis-Hillman adducts in the presence of samarium metal-trimethylsilyl chloride under mild conditions. Presumably, the diselenides are cleaved by Sm/TMSCI system to form selemde anions, which then undergo SN2＇ substitution of Baylis-Hillman adducts to produce the （Z）-allyl selenides.

Samarium(II) Diiodide Induced Polarity Inversion of π-Allyl Palladium Complexes: The Formation of Allylic Selenides

Allylic acetates were reduced with Pd(0)-SmI2 in the presence of ArSeBr to form corresponding allylic selenides in good yields.

MOF-derived molybdenum selenide on Ti_(3)C_(2)T_(x) with superior capacitive performance for lithium-ion capacitors

Two-dimensional Ti_(3)C_(2)T_(x) exhibits outstanding rate property and cycle performance in lithium-ion capacitors(LICs)due to its unique layered structure,excellent electronic conductivity,and high specific surface area.However,like graphene,Ti_(3)C_(2)T_(x) restacks during electrochemical cycling due to hydrogen bonding or van der Waals forces,leading to a decrease in the specific surface area and an increase in the diffusion distance of electrolyte ions between the interlayer of the material.Here,a transition metal selenide MoSe_(2) with a special three-stacked atomic layered structure,derived from metal-organic framework(MOF),is introduced into the Ti_(3)C_(2)T_(x) structure through a solvo-thermal method.The synergic effects of rapid Li+diffusion and pillaring effect from the MoSe_(2) and excellent conductivity from the Ti_(3)C_(2)T_(x) sheets endow the material with excellent electrochemical reaction kinetics and capacity.The composite Ti_(3)C_(2)T_(x)@MoSe_(2) material exhibits a high capacity over 300 mAh·g^(-1) at 150 mA·g^(-1) and excellent rate property with a specific capacity of 150 mAh·g^(-1) at 1500 mA·g^(-1).Addition-ally,the material shows a superior capacitive contribution of 86.0%at 2.0 mV·s^(-1) due to the fast electrochemical reactions.A Ti_(3)C_(2)T_(x)@MoSe_(2)//AC LIC device is also fabricated and exhibits stable cycle performance.

A Superaerophobic Bimetallic Selenides Heterostructure for Efficient Industrial-Level Oxygen Evolution at Ultra-High Current Densities

Cost-effective and stable electrocatalysts with ultra-high current densities for electrochemical oxygen evolution reaction(OER)are critical to the energy crisis and environmental pollution.Herein,we report a superaerophobic three dimensional(3D)heterostructured nanowrinkles of bimetallic selenides consisting of crystalline NiSe2 and NiFe2Se4 grown on NiFe alloy(NiSe2/NiFe2Se4@NiFe)prepared by a thermal selenization procedure.In this unique 3D heterostructure,numerous nanowrinkles of NiSe2/NiFe2Se4 hybrid with a thickness of ~100 nm are grown on NiFe alloy in a uniform manner.Profiting by the large active surface area and high electronic conductivity,the superaerophobic NiSe2/NiFe2Se4@NiFe heterostructure exhibits excellent electrocatalytic activity and durability towards OER in alkaline media,outputting the low potentials of 1.53 and 1.54 V to achieve ultra-high current densities of 500 and 1000 mA cm^−2,respectively,which is among the most active Ni/Fe-based selenides,and even superior to the benchmark Ir/C catalyst.The in-situ derived FeOOH and NiOOH species from NiSe2/NiFe2Se4@NiFe are deemed to be efficient active sites for OER.

Phase transition and high temperature thermoelectric properties of copper selenide Cu_(2-x) Se (0 ≤ x ≤ 0.25)

With good electrical properties and an inherently complex crystal structure, Cu2-xSe is a potential ＂phonon glass electron crystal＂ thermoelectric material that has previously not attracted much interest. In this study, Cu2-xSe （0 ≤ x ≤0.25） compounds were synthesized by a melting-quenching method, and then sintered by spark plasma sintering to obtain bulk material. The effect of Cu content on the phase transition and thermoelectric properties of Cu2-xSe were investigated in the temperature range of 300 K-750 K. The results of X-ray diffraction at room temperature show that Cu2-xSe compounds possess a cubic structure with a space group of Fm3m （#225） when 0.15 〈 x ≤ 0.25, whereas they adopt a composite of monoclinic and cubic phases when 0 ≤x ≤ 0.15. The thermoelectric property measurements show that with increasing Cu content, the electrical conductivity decreases, the Seebeck coefficient increases and the thermal conductivity decreases. Due to the relatively good power factor and low thermal conductivity, the nearly stoichiometric Cu2Se compound achieves the highest ZT of 0.38 at 750 K. It is expected that the thermoelectric performance can be further optimized by doping appropriate elements and/or via a nanostructuring approach.

Carbon-Coated Three-Dimensional MXene/Iron Selenide Ball with Core–Shell Structure for High-Performance Potassium-Ion Batteries

Two-dimensional(2D)MXenes are promising as electrode materials for energy storage,owing to their high electronic conductivity and low diffusion barrier.Unfortunately,similar to most 2D materials,MXene nanosheets easily restack during the electrode preparation,which degrades the electrochemical performance of MXene-based materials.A novel synthetic strategy is proposed for converting MXene into restacking-inhibited three-dimensional(3D)balls coated with iron selenides and carbon.This strategy involves the preparation of Fe_(2)O_(3)@carbon/MXene microspheres via a facile ultrasonic spray pyrolysis and subsequent selenization process.Such 3D structuring effectively prevents interlayer restacking,increases the surface area,and accelerates ion transport,while maintaining the attractive properties of MXene.Furthermore,combining iron selenides and carbon with 3D MXene balls offers many more sites for ion storage and enhances the structural robustness of the composite balls.The resultant 3D structured microspheres exhibit a high reversible capacity of 410 mAh g^(−1) after 200 cycles at 0.1 A g^(−1) in potassium-ion batteries,corresponding to the capacity retention of 97% as calculated based on 100 cycles.Even at a high current density of 5.0 A g^(−1),the composite exhibits a discharge capacity of 169 mAh g^(−1).

Nitrogen-Doped Carbon-Encased Bimetallic Selenide for High-Performance Water Electrolysis

Demand of highly efficient earth-abundant transition metal-based electrocatalysts to replace noble metal materials for boosting oxygen evolution reaction(OER)is rapidly growing.Herein,an electrochemically exfoliated graphite(EG)foil supported bimetallic selenide encased in N-doped carbon(EG/(Co,Ni)Se2-NC)hybrid is developed and synthesized by a vapor-phase hydrothermal strategy and subsequent selenization process.The as-prepared EG/(Co,Ni)Se2-NC hybrid exhibits a core-shell structure where the particle diameter of(Co,Ni)Se2 core is about 70 nm and the thickness of N-doped carbon shell is approximately 5 nm.Benefitting from the synergistic effects between the combination of highly active Co species and improved electron transfer from Ni species,and N-doped carbon,the EG/(Co,Ni)Se2-NC hybrid shows remarkable electrocatalytic activity toward OER with a comparatively low overpotential of 258 mV at an current density of 10 mA cm?2 and a small Tafel slope of 73.3 mV dec?1.The excellent OER catalysis performance of EG/(Co,Ni)Se2-NC hybrid is much better than that of commercial Ir/C(343 mV at 10 mA cm?2 and 98.1 mV dec?1),and even almost the best among all previously reported binary CoNi selenide-based OER electrocatalysts.Furthermore,in situ electrochemical Raman spectroscopy combined with ex situ X-ray photoelectron spectroscopy analysis indicates that the superb OER catalysis activity can be attributed to the highly active Co-OOH species and modified electron transfer process from Ni element.

In Situ Monitoring the Potassium‑Ion Storage Enhancement in Iron Selenide with Ether‑Based Electrolyte

As one of the promising anode materials,iron selenide has received much attention for potassium-ion batteries(KIBs).Nevertheless,volume expansion and sluggish kinetics of iron selenide result in the poor reversibility and stability during potassiation–depotassiation process.In this work,we develop iron selenide composite matching ether-based electrolyte for KIBs,which presents a reversible specific capacity of 356 mAh g^(−1) at 200 mA g^(−1) after 75 cycles.According to the measurement of mechanical properties,it is found that iron selenide composite also exhibits robust and elastic solid electrolyte interphase layer in ether-based electrolyte,contributing to the improvement in reversibility and stability for KIBs.To further investigate the electrochemical enhancement mechanism of ether-based electrolyte in KIBs,we also utilize in situ visualization technique to monitor the potassiation–depotassiation process.For comparison,iron selenide composite matching carbonate-based electrolyte presents vast morphology change during potassiation–depotassiation process.When changing to ether-based electrolyte,a few minor morphology changes can be observed.This phenomenon indicates an occurrence of homogeneous electrochemical reaction in ether-based electrolyte,which results in a stable performance for potassium-ion(K-ion)storage.We believe that our work will provide a new perspective to visually monitor the potassium-ion storage process and guide the improvement in electrode material performance.

Sulfur-modified nickel selenide as an efficient electrocatalyst for the oxygen evolution reaction

The sluggish four-electron transfer of the oxygen evolution reaction(OER)limits the performance of water electrolyzers.Hence,OER electrocatalysts based on earth-abundant elements are urgently needed.Heteroatom doping has been an efficient approach to boost the intrinsic OER activity of the active sites by modifying the electronic structure.Here,a simple anion substitution strategy is reported that increases the OER activity of nickel selenides via a one-step hydrothermal treatment of a metal–organic framework precursor.The resulting S-substituted Ni_(3)Se_(4) nanoparticles display distortion of their crystal lattice.As expected,the sulfur substitution modifies the electronic structure of Ni_(3)Se_(4) and leads to outstanding electrocatalytic activity.All the S-substituted Ni_(3)Se_(4) catalysts exhibit higher OER activities than the original Ni_(3)Se_(4).The optimized catalyst achieves a current density of 10 mA cm^(−2) at an overpotential of 275 mV with a Tafel slope of 64 mV dec^(−1) in 1.0 M KOH.In addition to its electrochemical activity,the S-Ni_(3)Se_(4)-2 catalyst also exhibits good stability with only a 7.5%increase in overpotential at 50 mA cm^(−2) after 100 hours.This work demonstrates one strategy to modify the electronic structure of transition metal compounds by anion regulation.

Development of antimony sulfide–selenide Sb2(S,Se)3-based solar cells

Antimony sulfide–selenide Sb2（S,Se）3,including Sb2S3and Sb2Se3,can be regarded as binary metal chalcogenides semiconductors since Sb2S3and Sb2Se3are isomorphous.They possess abundant elemental storage,nontoxicity,good stability with regard to moisture at elevated temperatures and suitable physical parameters for light absorption materials in solar cells.To date,quite a few attempts have been conducted in the materials synthesis,photovoltaic property investigation and device fabrication.Benefiting from previous investigation in thin film solar cells and new generation nanostructured solar cells,this class of materials has been applied in either sensitized-architecture or planar heterojunction solar cells.Decent power conversion efficiencies from 5%to 7.5%have been achieved.Apparently,further improvement on the efficiency is required for future practical applications.To give an overview of this research field,this paper displays some typical researches regarding the methodologies toward the antimony sulfide–selenide synthesis,development of interfacial materials and device fabrications,during which we highlight some critical findings that promote the efficiency enhancement.Finally,this paper proposes some outstanding issue regarding fundamental understanding of the materials,some viewpoints for the efficiency improvement and their future challenges in solar cell applications.

Two-in-one shell configuration for bimetal selenides toward fast sodium storage within broadened voltage windows

The shell structure design has been recognized as a highly efficient strategy to buffer the severe volume expansion and consecutive pulverization of conversion-type anodes.Nevertheless,construction of a functional shell with a stabilized structure that meets the demands of both high electronic conductivity and feasible pathways for Na^(+)ions has been a challenge so far.Herein,we design a two-in-one shell configuration for bimetal selenides to achieve fast sodium storage within broadened voltage windows.The hybridized shell,which benefits from the combination of titanium dioxide quantum dots and amorphous carbon,can not only effectively buffer the strain and maintain structural integrity but also allow facile and reversible transport of electrons and Na^(+)uptake for electrode materials during sodiation/desodiation processes,resulting in increased reaction kinetics and diffusion of sodium ions,conferring many benefits to the functionality of conversion-type electrode materials.As a representative material,Ni-CoSe_(2) with such structural engineering shows a reversible capacity of 515 mAh g^(−1)at 0.1 A g^(−1)and a stable capacity of 416 mAh g^(−1)even at 6.4 A g^(−1);more than 80%of the capacity at 0.1 A g^(−1)could be preserved,so that this strategy holds great promise for designing fast-charging conversion-type anodes in the future.

Metal selenides for photocatalytic Z-scheme pure water splitting mediated by reduced graphene oxide

Exploration of novel narrow bandgap semiconductors for overall water splitting is vital for the realization of practical solar H2 production. In the work, solid solutions of zinc selenide and copper gallium selenide with absorption edge wavelengths ranging from 480 to 730 nm were developed. Using these metal selenides as H2-evolving photocatalysts, CoOx/BiVO4 as the O2-evolving photocatalyst, and reduced graphene oxide as the electron mediator, all-solid-state Z-scheme overall pure water splitting systems were constructed. The rate of photocatalytic H2 evolution from aqueous solutions containing Na2S and Na2SO3 as the electron donors was evaluated while employing these selenide photocatalysts at various Zn/(Zn+Cu) and Ga/Cu molar ratios. The data demonstrate that efficient Z-scheme overall water splitting was significantly correlated to the photoelectrochemical performance of the selenide photocatalysts acting as photocathodes, rather than the photocatalytic activities of these materials during the sacrificial H2 evolution.

Efficient electrocatalytic overall water splitting and structural evolution of cobalt iron selenide by one-step electrodeposition

Developing bifunctional electrocatalysts with both high catalytic activity and high stability is crucial for efficient water splitting in alkaline media.Herein,a Fe-incorporated dual-metal selenide on nickel foam(Co_(0.9)Fe_(0.1)-Se/NF) is synthesized via a facile one-step electrodeposition method.As-synthesized materials could serve as self-supported bifunctional electrocatalysts with excellent catalytic activity towards oxygen evolution reaction(OER) and hydrogen evolution reaction(HER) in alkaline media.Experimental results show that delivering a 10 mA cm^(-2) water splitting current density only requires a cell voltage of 1.55 V.In addition,a very stable performance could be kept for about 36 hours,indicating their excellent working stability.Moreover,by means of phase analysis,we have identified that the evolution of the synthesized Co_(0.9)Fe_(0.1)-Se/NF experiences two entirely different processes in HER and OER,which hydroxide and oxyhydroxide are regarded as the real active sites,respectively.This work may pave the way to further understanding the relationships between the reactivity and stability of chalcogenide-based electrocatalysts and facilitating the rational design of efficient electrocatalysts for future renewable energy system applications.

Q-Switched Erbium-Doped Fiber Laser Using Cadmium Selenide Coated onto Side-Polished D-Shape Fiber as Saturable Absorber

A stable Q-switched erbium doped fiber laser emitting at 1558 nm is demonstrated using a cadmium selenide（CdSe） material coated onto a side-polished D-shape fiber as the saturable absorber（SA）. By elevating the input pump power from the threshold of 91 mW to the maximum available power of 136 mW, a pulse train with a maximum repetition rate of 57.44 kHz, minimum pulse width of 3.76 us, maximum average output power of7.99 mW, maximum pulse energy of 0.1391 uJ, and maximum peak power of 36.99 mW are obtained. The signalto-noise ratio of the spectrum is measured to be around 75 dB. This CdSe based SA is simple, robust, and reliable,and thus suitable for making a portable pulse laser source.

Electronic Phase Separation in Iron Selenide(Li,Fe)OHFeSe Superconductor System

The phenomenon of phase separation into antiferromagnetic（AFM） and superconducting（SC） or normal-state regions has great implication for the origin of high-temperature（high-T_c） superconductivity. However, the occurrence of an intrinsic antiferromagnetism above the T_c of（Li,Fe）OHFe Se superconductor is questioned. Here we report a systematic study on a series of（Li,Fe）OHFe Se single crystal samples with T_c up to ～41 K. We observe an evident drop in the static magnetization at T_（afm） ～ 125 K, in some of the SC（T_c 38 K, cell parameter c■9.27 ？） and non-SC samples. We verify that this AFM signal is intrinsic to（Li,Fe）OHFe Se. Thus, our observations indicate mesoscopic-to-macroscopic coexistence of an AFM state with the normal（below T_（afm）） or SC（below T_c） state in（Li,Fe）OHFe Se. We explain such coexistence by electronic phase separation, similar to that in high-T_c cuprates and iron arsenides. However, such an AFM signal can be absent in some other samples of（Li,Fe）OHFe Se, particularly it is never observed in the SC samples of T_c 38 K, owing to a spatial scale of the phase separation too small for the macroscopic magnetic probe. For this case, we propose a microscopic electronic phase separation. The occurrence of two-dimensional AFM spin fluctuations below nearly the same temperature as T_（afm）, reported previously for a（Li,Fe）OHFe Se（T_c ～ 42 K） single crystal, suggests that the microscopic static phase separation reaches vanishing point in high T_c（Li,Fe）OHFe Se. A complete phase diagram is thus established. Our study provides key information of the underlying physics for high-T_c superconductivity.