To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate elect...To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate electrolyte to form a dual-salt system.The optimization mechanism enhancing the fast-charging capability of LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)(NCM523)cathode is systematically explored.Molecular dynamics simulations and electrochemical characterization demonstrate the reconstruction of Li+solvation structures,expanding the voltage window and reducting Li^(+)desolvation barriers.In addition,the incorporation of LiDFOB induces the generation of a LiF/Li_(x)BO_(y)F_(z)-enriched cathode-electrolyte interphase,which effectively suppresses the dissolution of transition metals.In situ impedance measurements reveal the accelerated interfacial charge transfer kinetics.As expected,the NCM523 cathode achieves an 82%state-of-charge(SOC)in 12 min at 5 C(25°C)with 87%capacity retention after 100 cycles,and exhibits a 65%higher discharge capacity at 1 C than the baseline at−20°C.The 1 Ah pouch cells based on LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)cathodes,graphite anodes,and 0.5 wt%LiDFOB-modified electrolyte demonstrate fast-charging capabilities:charging 97%of the pouch cell capacity within 30 min(2 C)and 80%within 15 min(4 C)at 25°C.This study offers a practical electrolyte design strategy that enhances the fast-charging performance of lithium-ion batteries(LIBs)over a wide temperature range(from−20 to 25°C).展开更多
Promising aqueous zinc metal batteries(AZMBs)continue to face significant challenges regarding zinc anode reversibility due to detrimental reactions including hydrogen evolution and corrosion.Herein,the d-band center ...Promising aqueous zinc metal batteries(AZMBs)continue to face significant challenges regarding zinc anode reversibility due to detrimental reactions including hydrogen evolution and corrosion.Herein,the d-band center is used as an“intuitive descriptor”to compare the hydrogen evolution activity of zinc-based transition bimetallic oxides(ZTBOs)of fourth-period transition metal elements,and the advantages of ZnTi_(3)O_(7)(ZTO)functional protective layer in inhibiting hydrogen evolution and extending the lifespan of the zinc anode are selectively identified.展开更多
Phosphorus is the potential anode material for emerging potassium-ion batteries(PIBs)owing to the highest specific capacity and relatively low operation plateau.However,the reversible delivered capacities of phosphoru...Phosphorus is the potential anode material for emerging potassium-ion batteries(PIBs)owing to the highest specific capacity and relatively low operation plateau.However,the reversible delivered capacities of phosphorus-based anodes,in reality,are far from the theoretical capacity corresponding to the formation of K3P alloy.And,their underlying potassium storage mechanisms remain poorly understood.To address this issue,for the first time,we perform high-resolution solid-state31P NMR combined with XRD measurements,and density functional theory calculations to yield a systemic quantitative understanding of(de)potassiation reaction mechanism of phosphorus anode.We explicitly reveal a previously unknown asymmetrical nanocrystalline-to-amorphous transition process via rP←→(K_(3)P_(11),K_(3)P_(7),beta-K_(4)P_(6))←→(alpha-K4P6)←→(K_(1-x)P,KP,K_(4-x)P3,K_(1+x)P)←→(amorphous K4P3,amorphous K3P)that are proceed along with the electrochemical potassiation/depotassiation processes.Additionally,the corresponding KP alloys intermediates,such as the amorphous phases of K_(4)P_(3),K_(3)P,and the nonstoichiometric phases of“K_(1-x)P”,“K_(1+x)P”,“K_(4-x)P_(3)”are experimentally detected,which indicating various complicated K-P alloy species are coexisted and evolved with the sluggish electrochemical reaction kinetics,resulting in lower capacity of phosphorus-based anodes.Our findings offer some insights into the specific multi-phase evolution mechanism of alloying anodes that may be generally involved in conversion-type electrode materials for PIBs.展开更多
High entropy alloys(HEAs)have been the star materials in electrocatalysis research in recent years.One of their key features is the greatly increased multiplicity of active sites compared to conventional catalytic mat...High entropy alloys(HEAs)have been the star materials in electrocatalysis research in recent years.One of their key features is the greatly increased multiplicity of active sites compared to conventional catalytic materials.This increased multiplicity stimulates a cocktail effect and a scaling-relation breaking effect,and results in improved activity.However,the multiplicity of active sites in HEAs also poses new problems for mechanistic studies.One apparent problem is the inapplicability to HEA catalysts of the currently most popular mechanistic study method,which uses the electrocatalytic theoretical framework(ETF)based on the computational hydrogen electrode(CHE).The ETF uses a single adsorption energy to represent the catalyst,i.e.,a catalyst is represented by a'point'in the volcanic relationship.It naturally does not involve the multiplicity of active sites of a catalyst,and hence loses brevity in expressing the cocktail effect and scaling-relation breaking effect in HEA catalysis.This paper attempts to solve this inapplicability.Based on the fact that the adsorption energy distribution of HEAs is close to a normal distribution,the mean and variance of the adsorption energy distribution are introduced as descriptors of the ETF,replacing the original single adsorption energy.A quantitative relationship between the variance and the cocktail and scaling-relation braking effects is established.We believe the method described in this work will make the ETF more effective in mechanistic studies of HEA electrocatalysis.展开更多
Single-band red upconversion luminescence(UCL) is vital to in vivo bioimaging as well as "see and treat" biomedicines. Herein, starting with the previously reported β-NaErF4:Tm UCNPs, we examined the effect...Single-band red upconversion luminescence(UCL) is vital to in vivo bioimaging as well as "see and treat" biomedicines. Herein, starting with the previously reported β-NaErF4:Tm UCNPs, we examined the effects of both Yb^(3+) doping and inert shell coating on the red-to-green(R/G) ratio for Er3+ based UCL. The doping of Yb^(3+) into the β-NaErF4:Tm3+ core not only enhances the whole UCL intensity, but also raises the R/G ratio by 1.25 times. In addition, the coating of an inert NaYF4 shell, which is usually adopted for the enhancement of UCL intensity, further boosts the R/G value up to as high as 77.92. This work may benefit the potential bioimaging application of single-band red UCL.展开更多
Ion-absorbed rare earth ores radioactive residues(IREORR)are a class of waste residue from the production of rare earth elements(REEs).Because of its radioactive dose,IREORR are usually stored in waste warehouses.IREO...Ion-absorbed rare earth ores radioactive residues(IREORR)are a class of waste residue from the production of rare earth elements(REEs).Because of its radioactive dose,IREORR are usually stored in waste warehouses.IREORR are difficult to be disposed of.However,it contains relatively high concentrations of REEs,which can be considered as a valuable secondary resource.In this paper,a novel process is developed for the separation of thorium(Th)and recovery of REEs from IREORR hydrochloric acid leachate with primary amine N1923 and Cyanex?572,respectively.The effects of sulfate concentration,extractant concentration and pH on N1923 extraction in hydrochloric acid solution were investigated in detail.The results show that the extraction capacity of N1923 can be improved by adding sulfate to the solution and increasing the concentration of N1923.Acidity has little effect on the extraction of Th when pH is higher than 1.As for the stripping,REEs are more easily stripped from loaded organic phase than Th,and nitric acid is a better stripping agent than hydrochloric acid.Combined with the extraction of Cyanex■572 for REEs,a fractional extraction experiment for separating Th and enriching of REEs was performed.The yield of Th is higher than 99.9%and the concentration of REEs is enriched to 183.84 g/L.展开更多
Lanthanide doped fluorescent nanoparticles have gained considerable attention in biomedical applications.However,the low uptake efficiency of nanoparticles by cells has limited their applications.In this work,we demon...Lanthanide doped fluorescent nanoparticles have gained considerable attention in biomedical applications.However,the low uptake efficiency of nanoparticles by cells has limited their applications.In this work,we demonstrate how the uptake efficiency is affected by the size of nanoparticles under flow conditions.Using the same size NaYF_(4):20%Yb^(3+),2%Er^(3+),2%Ce^(3+)(the contents of rare earths elements are in molar fraction)nanoparticles as core,NaYF_(4):20%Yb^(3+),2%Er^(3+),2%Ce^(3+)@NaYF_(4) core-shell structured nanorods(NRs)with different sizes of 60-224 nm were synthesized by thermal decomposition and hot injection method.Under excitation at 980 nm,a strong upconversion green emission(541 nm,^(2)H_(11/2)→^(4) I_(15/2) of Er^(3+))is observed for all samples.The emission intensity for each size nanorod was calibrated and is found to depend on the width of NRs.Under flow conditions,the nanorods with 96 nm show a maximum uptake efficiency by endothelial cells.This work demonstrates the importance of optimizing the size for improving the uptake efficiency of lanthanide-doped nanoparticles.展开更多
A novel type of extraction-precipitation strategy based on phosphate was developed to recover rare earth(RE,i.e.,La,Ce,Nd,and Pr)from waste nickel-metal hydride(NiMH)batteries.This method does not require saponificati...A novel type of extraction-precipitation strategy based on phosphate was developed to recover rare earth(RE,i.e.,La,Ce,Nd,and Pr)from waste nickel-metal hydride(NiMH)batteries.This method does not require saponification and organic solvents.The novel phosphates,i.e.,dibenzyl phosphate(DBP),diphenyl phosphate(DPP),triphenyl phosphate(TPP)were studied as extraction-precipitants.DBP has high precipitation efficiencies for RE^(3+),which can reach 97.84%,100%,100%and 99.77%,respectively.In addition,the precipitation efficiencies of Mn^(2+),Co^(2+)and Ni^(2+)are less than 1.75%.DBP-RE has the largest particle size(D10=52.6μm,D50=135.35μm,D90=296.08μm),which is much larger than the precipitations formed by NH_(4)HCO_(3),H_(2)C2O_(4),CaO and MgO.The larger precipitation particle sizes contribute to improving the solid-liquid separation efficiency.With 3 mol/L hydrochloric acid,the stripping efficiency of DBP-RE reaches 98.60%,and the purity of recovered RE is 99.85%.The regenerated DBP can be directly used for the recycling extraction.Therefore,the novel extraction-precipitation strategy is a green and sustainable separation method.展开更多
Hybrid materials are attracting intensive attention for their applications in electronics, photoelectronics, LEDs, field-effect transistors, etc. Engineering new hybrid materials and further exploiting their new funct...Hybrid materials are attracting intensive attention for their applications in electronics, photoelectronics, LEDs, field-effect transistors, etc. Engineering new hybrid materials and further exploiting their new functions will be significant for future science and technique development. In this work, alternatively stacked self-assembled CoAl LDH/MoS2 nanohybrid has been successfully synthesized by an exfoliation-flocculation method from positively charged CoAl LDH nanosheets（CoAl-NS） with negatively charged MoS2 nanosheets（MoS2-NS）. The CoAl LDH/MoS2 hybrid material exhibits an enhanced catalytic performance for oxygen evolution reaction（OER） compared with original constituents of CoAl LDH nanosheets and MoS2 nanosheets. The enhanced OER catalytic performance of CoAl LDH/MoS2 is demonstrated to be due to the improved electron transfer, more exposed catalytic active sites, and accelerated oxygen evolution reaction kinetics.展开更多
Mg-A1-C1 layered double hydroxide （C1-LDH） was prepared to simultaneously remove Cu（II） and Cr（VI） from aqueous solution. The coexisting Cu（II） （20 mg/L） and Cr（VI） （40 mg/L） were completely removed with...Mg-A1-C1 layered double hydroxide （C1-LDH） was prepared to simultaneously remove Cu（II） and Cr（VI） from aqueous solution. The coexisting Cu（II） （20 mg/L） and Cr（VI） （40 mg/L） were completely removed within 30 min by C1-LDH in a dosage of 2.0 g/L; the removal rate of Cu（II） was accelerated in the presence of cr（VI）. Moreover, compared with the adsorption of single Cu（II） or Cr（VI）, the adsorption capacities of C1-LDH for Cu（II） and Cr（VI） can be improved by 81.05% and 49.56%, respectively, in the case of coexisting Cu（II） （200 mg/L） and Cr（VI） （400 mg/L）. The affecting factors （such as solution initial pH, adsorbent dosage, and contact time） have been systematically investigated. Besides, the changes of pH values and the concentrations of Mg2＋ and A13＋ in relevant solutions were monitored. To get the underlying mechanism, the C1-LDH samples before and after adsorption were thoroughly characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. On the basis of these analyses, a possible mechanism was proposed. The coadsorption process involves anion exchange of Cr（VI） with C1- in C1-LDH interlayer, isomorphic substitution of Mg2＋ with Cu2＋, formation of Cu2CI（OH）3 precipitation, and the adsorption of Cr（VI） by Cu2CI（OH）3. This work provides a new insight into simultaneous removal of heavy metal cations and anions from wastewater by CI-LDH.展开更多
A binuclear cuprous complex [Cu（μ-I）（NPPh）]2（1,NPPh = 1-（2-（diphenylphosphanyl）phenyl）-3-phenyl-4,5-dihydro-1 H-pyrazole） was synthesized and characterized by elemental analysis,NMR and X-ray single-crystal...A binuclear cuprous complex [Cu（μ-I）（NPPh）]2（1,NPPh = 1-（2-（diphenylphosphanyl）phenyl）-3-phenyl-4,5-dihydro-1 H-pyrazole） was synthesized and characterized by elemental analysis,NMR and X-ray single-crystal structure analysis.It crystallizes in triclinic space group P2_1/n with a = 10.7520（3）,b = 18.1860（5）,c = 11.8487（3） ？,β = 91.864（2）,V = 2315.61（11） ？~3,Z = 4,Mr = 594.87,Dc = 1.706 g/cm^3,F（000） = 1176.0,μ = 12.582 mm（-1）,GOOF = 1.048,the final R = 0.0289 and wR = 0.0670 for 3787 observed reflections with I 〉 2σ（I）.The Cu atoms in the complex are four-coordinated and adopt distorted tetrahedral coordination geometry.In the solid state,the complex exhibits greenish yellow photoluminescence with a peak maximum of 533 nm,a decay time of 34 μs,and a photoluminescence quantum yield of 63.6% at room temperature,respectively.展开更多
Fe/N/C catalysts,synthesized through the pyrolysis of Fe-doped metal–organic framework (MOF) precursors,have attracted extensive attention owing to their promising oxygen reduction reaction (ORR) catalytic activity i...Fe/N/C catalysts,synthesized through the pyrolysis of Fe-doped metal–organic framework (MOF) precursors,have attracted extensive attention owing to their promising oxygen reduction reaction (ORR) catalytic activity in fuel cells and/or metal-air batteries.However,post-treatments (acid washing,second pyrolysis,and so on) are unavoidable to improve ORR catalytic activity and stability.The method for introducing Fe^(3+) sources (anhydrous Fe Cl_(3)) into the MOF structure,in particular,is a critical step that can avoid time-consuming post-treatments and result in more exposed Fe-N_(x) active sites.Herein,three different Fe doping strategies were systematically investigated to explore their influence on the types of active sites formed and ORR performance.Fe-NC(Zn^(2+)),synthesized by one-step pyrolysis of Fe doped ZIF-8 (Zn^(2+)) precursor which was obtained by adding the anhydrous Fe Cl_(3)source into the Zn(NO_(3))_(2)·6H_(2)O/methanol solution before mixing,possessed the highest Fe-N_(x)active sites due to the high-efficiency substitution of Zn^(2+)ions with Fe^(3+) ions during ZIF-8 growth,the strong interaction between Fe^(3+) ions and N atoms of 2-Methylimidazole (2-MIm),and ZIF-8’s micropore confinement effect.As a result,Fe-NC(Zn^(2+)) presented high ORR activity in the entire p H range (p H=1,7,and 13).At p H=13,Fe-NC(Zn^(2+)) exhibited a half-wave potential (E1/2) of 0.95 V (vs.reversible hydrogen electrode),which was 70 m V higher than that of commercial Pt/C.More importantly,Fe-NC(Zn^(2+)) showed superior ORR stability in neutral media without performance loss after 5,000 cycles.A record-high open-circuit voltage(1.9 V) was obtained when Fe-NC(Zn^(2+)) was used as a cathodic catalyst in assembled Mg-air batteries in neutral media.The assembled liquid and all-solid Mg-air batteries with high performance indicated that Fe-NC(Zn^(2+)) has enormous potential for use in flexible and wearable Mg-air batteries.展开更多
Electrolytic water splitting,as a promising route to hydrogen(H_(2))production,is still confronted with the sluggish anodic oxygen evolution reaction(OER)and its less value-added O2 production.Herein,we report a bifun...Electrolytic water splitting,as a promising route to hydrogen(H_(2))production,is still confronted with the sluggish anodic oxygen evolution reaction(OER)and its less value-added O2 production.Herein,we report a bifunctional electrode fabricated by in situ growth of Mn-doped CoSe_(2)nanonetworks on carbon fiber cloth(Mn-CoSe_(2)/CFC),which shows attractive electrocatalytic properties toward glycerol oxidation reaction(GOR)in alkali and hydrogen evolution reaction(HER)in acid.A flow alkali/acid hybrid electrolytic cell(fA/A-hEC)was then developed by coupling anodic GOR with cathodic HER with the Mn-CoSe_(2)/CFC bifunctional electrode.Such fA/A-hEC enables a rather low voltage of 0.54 V to achieve 10 mA cm^(-2),and maintain long-term electrolysis stability over 300-h operation at 100 mA cm^(-2)with Faraday efficiencies of over 99%for H_(2)and 90%for formate production.The designed bifunctional electrode in such innovative fA/A-hEC device provides insightful guidance for coupling energy-efficient hydrogen production with biomass upgradation.展开更多
Partial substitution of polyoxometalate(POM)is an efficient route to modulate the catalytic property of maternal POM.In this work,a new Keggin type POM involving{Ni 6}cluster,{[Ni(H_(2)O)_(2)(Dach)_(2)][Ni(Dach)_(2)]_...Partial substitution of polyoxometalate(POM)is an efficient route to modulate the catalytic property of maternal POM.In this work,a new Keggin type POM involving{Ni 6}cluster,{[Ni(H_(2)O)_(2)(Dach)_(2)][Ni(Dach)_(2)]_(2)}{[Ni_(6)Cl(μ-OH)_(3)(H_(2)O)(Dach)_(3)(WO_(4))(PW9 O_(3)_(4))][Ni_(6)(μ-OH)_(3)(H_(2)O)_(2)(Dach)_(3)(WO_(4))(PW9 O_(3)_(4))]}Cl·27H_(2)O,(1,Dach=1,2-diaminocyclohexane)was synthesized.Compounds 1 shows excellent catalytic performance in the selective oxidation of aniline to azoxybenzene(AOB)in water.The apparently different results from that with the matrix{PW_(9)O_(34)}({PW9})suggest the successful regulation of the catalytic property of{PW9}by the introduction of the{Ni6}cluster into the skeleton.The experimental results indicate that the highlighted performance of 1 is contributed by the synergy of W and Ni sites,which are respectively responsible for the oxidation and condensation steps in the production of AOB.The good selectivity to AOB is essentially attributed to the effective modulation of the reaction rates of oxidation and condensation steps by W and Ni sites,respectively.展开更多
Full-spectrum phosphor-converted white-light-emitting diodes(pc-WLED)are emerging as a mainstream technology in semiconductor lighting.Nevertheless,high-performance blue phosphor which can be excited efficiently by a ...Full-spectrum phosphor-converted white-light-emitting diodes(pc-WLED)are emerging as a mainstream technology in semiconductor lighting.Nevertheless,high-performance blue phosphor which can be excited efficiently by a 400 nm NUV diode chip is still lacking.Herein,we present a blue-emitting Na_(3)KMg_(7)(PO_(4))6:Eu^(2+)phosphor synthesized by the solid-reaction method.Particularly,we find that the using of Li_(2)CO_(3)as flux can significantly improve the crystal quality and thus the emission efficiency of the phosphor.Meanwhile,the excitation peak of the phosphor shifts from 365 to 400 nm,which is pivotal for efficient NUV(400 nm)diode chip excitation.The practical Eu^(2+)concentration is also enhanced by using Li_(2)CO_(3)as flux,and the absorption efficiency is greatly increased.This phosphor exhibits superior PL thermal stability,namely retains 94%integrated photoluminescence intensity at 150℃of that at 25℃.As a result,the optimized phosphor shows an emission band peaked at 437 nm with a bandwidth of 40 nm and a high external photoluminescence quantum yield of 51.7%.Finally,a pc-WLED was fabricated by using NKMPO:Eu^(2+)blue,Sr_(2)SiO_(4):Eu^(2+)green,CaAlSiN_(3):Eu^(2+)red phosphors,and a 400 nm NUV diode chip.It shows a high color rendering index of R_(a)=96.4 and a correlated color temperature of 4358 K.These results prove that NKMPO:Eu^(2+)is a promising blue phosphor for full-spectrum WLED based on NUV diode chips.展开更多
A cuprous dimer [Cu（POP）]2（pz4B）BF4·（CH3CN）3 （1, POP = bis（2-（diphenylphosphanyl）phenyl）ether, pz4B- = tetrakis（pyrazol-i-yl）borate anion） was synthesized from the reaction of Cu（CH3CN）4BF4, POP a...A cuprous dimer [Cu（POP）]2（pz4B）BF4·（CH3CN）3 （1, POP = bis（2-（diphenylphosphanyl）phenyl）ether, pz4B- = tetrakis（pyrazol-i-yl）borate anion） was synthesized from the reaction of Cu（CH3CN）4BF4, POP and Kpz4B in CH3CN at room temperature. The compound was characterized by elemental analysis and X-ray single-Crystal structure analysis. It crystallizes in monoclinic, space group P21/c with a = 12.3491（2）, b = 20.8845（3）, c = 33.0657（4） A, β = 94.251（1）°, V = 8504.3（2） A3, Z = 4, Mr = 1693.21, Dc = 1.322 g/cm3, F（000） = 3496,μ = 1.843 mm-1, GOOF = 1.031, the final R = 0.0442 and wR = 0.1235 for 14397 observed reflections with 1〉 2σ（I）. 1 is an ionic compound. It is composed of a BF4- anion and a {[Cu（POP）]2（pz4B）}＋ cation. The cation contains two [Cu（POP）]＋ cationic moieties and a pz4B- anionic linker. The Cu（I） ions show a distorted tetrahedral coordination geometry defined by two nitrogen atoms from a pz4B- bridging ligand and two phosphorous atoms from a POP terminal chelating ligand. The complex emits blue luminescence with the maximum peak at 457 nm with 3% quantum yield in solid state at room temperature. The Cu（I） centers are essentially electronically separated because both HOMO and LUMO contain very little contribution from the bridging ligand. The unexpected low emission is ascribed to the intramolecular interaction of the emissive centers.展开更多
Constructing layered-spinel composites is important to improve the rate performance of lithium-rich layered oxides.However,up to now,the effect of microstructure of composites on the rate performance has not been well...Constructing layered-spinel composites is important to improve the rate performance of lithium-rich layered oxides.However,up to now,the effect of microstructure of composites on the rate performance has not been well investigated.In this study,a series of samples were prepared by a simple protonation and de-protonation for the pristine layered material(LiMnNiCoO)obtained by sol-gel method.The characterizations of XRD,Raman and oxidation-reduction potentials of charge-discharge curves demonstrated that these samples after de-protonation are layered-spinel composites.When these composites were tested as a cathode of lithium-ion batteries,the sample treated with 0.1 M of nitric acid exhibited higher discharge capacities at each current density than that of other composites.The outstanding rate performance is attributed to the high concentration of conduction electron resulting from the low average valence state(44.2%of Ni)as confirmed by its high conductivity(1.124×10??mat39800Hz)and ambient temperature magnetic susceptibility(8.40×10emu/Oe?mol).This work has a guiding significance for the synthesis of high rate performance of lithium battery cathode materials.展开更多
Using the bottom-up method, we synthesized a series of perfluorinated covalent triazine-based frameworks(FCTFs) with porous structures for catalysis oxygen reduction reaction(ORR). The evolved FCTFs by high-temperatur...Using the bottom-up method, we synthesized a series of perfluorinated covalent triazine-based frameworks(FCTFs) with porous structures for catalysis oxygen reduction reaction(ORR). The evolved FCTFs by high-temperature carbonization show an apparent variation in electrocatalytic activity toward the ORR dependent on the type of F. The samples synthesized at 900 ℃(FCTF-900) exhibits advantages in terms of high activity, high durability, and methanol-tolerant as an efficient electrocatalyst for ORR, manifests a comparable or even better activity as compared with the commercial Pt/C catalysts not only in alkaline media but also in acidic and neutral electrolyte.展开更多
Electrosynthesis has recently attracted intensive research attentions and holds great potential in implementing scalable green synthesis thanks to more and more readily accessible renewable electric energy.
The detrimental“shuttle effect”of lithium polysulfides(LiPSs)together with sluggish multi-order reaction kinetics are the main drawbacks hindering lithium-sulfur(Li-S)batteries from commercial success.Here,we first ...The detrimental“shuttle effect”of lithium polysulfides(LiPSs)together with sluggish multi-order reaction kinetics are the main drawbacks hindering lithium-sulfur(Li-S)batteries from commercial success.Here,we first propose the implementability of layered rare-earth hydroxides(LREHs)in Li-S batteries to optimize electrochemical performance.In this work,a two-dimensional(2D)rare-earth-based composite constructed by the layered gadolinium hydroxy chloride[Gd_(2)(OH)_(5)(H_(2)O)_(n)]Cl nanoplates(LGdH NPs)and graphene oxide(GO)was designed as a sulfur immobilizer for Li-S batteries.Combining the experimental results and density functional theory(DFT)calculations,it is revealed that the LGdH@GO composite not only provides a strong anchoring of the intermediates during cycling,but also acts as an effective catalyst to accelerate the liquid-solid conversion of polysulfides.The Li-S batteries assembled by LGdH@GO modified separators delivered a superior rate performance with a specific capacity of 605.34 mAh/g at 5 C,as well as excellent cycle stability with a decay rate of 0.087%over 500 cycles at 2 C.This study provided a deep understanding of the mechanism to suppress the“shuttle effect”by the LREHs,and a guide to design effective functional interlayers for high-performance Li-S batteries with excellent electrocatalytic activity.展开更多
基金financially supported by the National Natural Science Foundation of China (Grant No. 52372191)the National Natural Science Foundation of China (Grant No. 22271106)+2 种基金the National Science Foundation of China (Grant Nos. 52073286 (C.-Z.L.), 22275185 (C.-Z.L.))the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ115 (C.-Z.L.)the XMIREM Autonomously Deployment Project (2023GG01 (C.-Z.L.))
文摘To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate electrolyte to form a dual-salt system.The optimization mechanism enhancing the fast-charging capability of LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)(NCM523)cathode is systematically explored.Molecular dynamics simulations and electrochemical characterization demonstrate the reconstruction of Li+solvation structures,expanding the voltage window and reducting Li^(+)desolvation barriers.In addition,the incorporation of LiDFOB induces the generation of a LiF/Li_(x)BO_(y)F_(z)-enriched cathode-electrolyte interphase,which effectively suppresses the dissolution of transition metals.In situ impedance measurements reveal the accelerated interfacial charge transfer kinetics.As expected,the NCM523 cathode achieves an 82%state-of-charge(SOC)in 12 min at 5 C(25°C)with 87%capacity retention after 100 cycles,and exhibits a 65%higher discharge capacity at 1 C than the baseline at−20°C.The 1 Ah pouch cells based on LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)cathodes,graphite anodes,and 0.5 wt%LiDFOB-modified electrolyte demonstrate fast-charging capabilities:charging 97%of the pouch cell capacity within 30 min(2 C)and 80%within 15 min(4 C)at 25°C.This study offers a practical electrolyte design strategy that enhances the fast-charging performance of lithium-ion batteries(LIBs)over a wide temperature range(from−20 to 25°C).
基金support from National Natural Science Foundation of China(52272198 and 22109163)。
文摘Promising aqueous zinc metal batteries(AZMBs)continue to face significant challenges regarding zinc anode reversibility due to detrimental reactions including hydrogen evolution and corrosion.Herein,the d-band center is used as an“intuitive descriptor”to compare the hydrogen evolution activity of zinc-based transition bimetallic oxides(ZTBOs)of fourth-period transition metal elements,and the advantages of ZnTi_(3)O_(7)(ZTO)functional protective layer in inhibiting hydrogen evolution and extending the lifespan of the zinc anode are selectively identified.
基金financially supported by National Nature Science Foundation of China(Grant No.22272175,21805278,52072323,52122211)the Fujian Science and Technology Planning Projects of China(2020T3022,2022T3067)+3 种基金the National Key R&D Program of China(No.2021YFB3500400)the Future-prospective and Stride-across Programs of Haixi Institutes,Chinese Academy of Sciences(No.CXZX-2022-GH02)the Youth Innovation Foundation of Xiamen City(Grant No.3502Z20206083)the Opening Project of PCOSS,Xiamen University(Grant No.202014)。
文摘Phosphorus is the potential anode material for emerging potassium-ion batteries(PIBs)owing to the highest specific capacity and relatively low operation plateau.However,the reversible delivered capacities of phosphorus-based anodes,in reality,are far from the theoretical capacity corresponding to the formation of K3P alloy.And,their underlying potassium storage mechanisms remain poorly understood.To address this issue,for the first time,we perform high-resolution solid-state31P NMR combined with XRD measurements,and density functional theory calculations to yield a systemic quantitative understanding of(de)potassiation reaction mechanism of phosphorus anode.We explicitly reveal a previously unknown asymmetrical nanocrystalline-to-amorphous transition process via rP←→(K_(3)P_(11),K_(3)P_(7),beta-K_(4)P_(6))←→(alpha-K4P6)←→(K_(1-x)P,KP,K_(4-x)P3,K_(1+x)P)←→(amorphous K4P3,amorphous K3P)that are proceed along with the electrochemical potassiation/depotassiation processes.Additionally,the corresponding KP alloys intermediates,such as the amorphous phases of K_(4)P_(3),K_(3)P,and the nonstoichiometric phases of“K_(1-x)P”,“K_(1+x)P”,“K_(4-x)P_(3)”are experimentally detected,which indicating various complicated K-P alloy species are coexisted and evolved with the sluggish electrochemical reaction kinetics,resulting in lower capacity of phosphorus-based anodes.Our findings offer some insights into the specific multi-phase evolution mechanism of alloying anodes that may be generally involved in conversion-type electrode materials for PIBs.
文摘High entropy alloys(HEAs)have been the star materials in electrocatalysis research in recent years.One of their key features is the greatly increased multiplicity of active sites compared to conventional catalytic materials.This increased multiplicity stimulates a cocktail effect and a scaling-relation breaking effect,and results in improved activity.However,the multiplicity of active sites in HEAs also poses new problems for mechanistic studies.One apparent problem is the inapplicability to HEA catalysts of the currently most popular mechanistic study method,which uses the electrocatalytic theoretical framework(ETF)based on the computational hydrogen electrode(CHE).The ETF uses a single adsorption energy to represent the catalyst,i.e.,a catalyst is represented by a'point'in the volcanic relationship.It naturally does not involve the multiplicity of active sites of a catalyst,and hence loses brevity in expressing the cocktail effect and scaling-relation breaking effect in HEA catalysis.This paper attempts to solve this inapplicability.Based on the fact that the adsorption energy distribution of HEAs is close to a normal distribution,the mean and variance of the adsorption energy distribution are introduced as descriptors of the ETF,replacing the original single adsorption energy.A quantitative relationship between the variance and the cocktail and scaling-relation braking effects is established.We believe the method described in this work will make the ETF more effective in mechanistic studies of HEA electrocatalysis.
基金Project supported by the National Key Research and Development Program of China(2016YFB0701003)the National Natural Science Foundation of China(51872288,11674318,51472242,21673242)
文摘Single-band red upconversion luminescence(UCL) is vital to in vivo bioimaging as well as "see and treat" biomedicines. Herein, starting with the previously reported β-NaErF4:Tm UCNPs, we examined the effects of both Yb^(3+) doping and inert shell coating on the red-to-green(R/G) ratio for Er3+ based UCL. The doping of Yb^(3+) into the β-NaErF4:Tm3+ core not only enhances the whole UCL intensity, but also raises the R/G ratio by 1.25 times. In addition, the coating of an inert NaYF4 shell, which is usually adopted for the enhancement of UCL intensity, further boosts the R/G value up to as high as 77.92. This work may benefit the potential bioimaging application of single-band red UCL.
基金supported by the National Key R&D Program of China(2017YFE0106900)Science and Technology Major Project of Ganzhou(2018)Fujian Program for High-Level Entrepreneurial and Innovative Talents Introduction and Science and Technology Service Network Initiative from Chinese Academy of Sciences。
文摘Ion-absorbed rare earth ores radioactive residues(IREORR)are a class of waste residue from the production of rare earth elements(REEs).Because of its radioactive dose,IREORR are usually stored in waste warehouses.IREORR are difficult to be disposed of.However,it contains relatively high concentrations of REEs,which can be considered as a valuable secondary resource.In this paper,a novel process is developed for the separation of thorium(Th)and recovery of REEs from IREORR hydrochloric acid leachate with primary amine N1923 and Cyanex?572,respectively.The effects of sulfate concentration,extractant concentration and pH on N1923 extraction in hydrochloric acid solution were investigated in detail.The results show that the extraction capacity of N1923 can be improved by adding sulfate to the solution and increasing the concentration of N1923.Acidity has little effect on the extraction of Th when pH is higher than 1.As for the stripping,REEs are more easily stripped from loaded organic phase than Th,and nitric acid is a better stripping agent than hydrochloric acid.Combined with the extraction of Cyanex■572 for REEs,a fractional extraction experiment for separating Th and enriching of REEs was performed.The yield of Th is higher than 99.9%and the concentration of REEs is enriched to 183.84 g/L.
基金Project supported by the Priority Research Platform Project of Xiamen(3502ZCQ20171002)the National Natural Science Foundation of China(11804338)。
文摘Lanthanide doped fluorescent nanoparticles have gained considerable attention in biomedical applications.However,the low uptake efficiency of nanoparticles by cells has limited their applications.In this work,we demonstrate how the uptake efficiency is affected by the size of nanoparticles under flow conditions.Using the same size NaYF_(4):20%Yb^(3+),2%Er^(3+),2%Ce^(3+)(the contents of rare earths elements are in molar fraction)nanoparticles as core,NaYF_(4):20%Yb^(3+),2%Er^(3+),2%Ce^(3+)@NaYF_(4) core-shell structured nanorods(NRs)with different sizes of 60-224 nm were synthesized by thermal decomposition and hot injection method.Under excitation at 980 nm,a strong upconversion green emission(541 nm,^(2)H_(11/2)→^(4) I_(15/2) of Er^(3+))is observed for all samples.The emission intensity for each size nanorod was calibrated and is found to depend on the width of NRs.Under flow conditions,the nanorods with 96 nm show a maximum uptake efficiency by endothelial cells.This work demonstrates the importance of optimizing the size for improving the uptake efficiency of lanthanide-doped nanoparticles.
基金Project supported by National Key R&D Program of China(2017YFE0106900)Key R&D Program of Jiangxi Province(S2020ZPYFG0029)Key Program of the Chinese Academy of Sciences(ZDRW-CN-2021-3-1-13)。
文摘A novel type of extraction-precipitation strategy based on phosphate was developed to recover rare earth(RE,i.e.,La,Ce,Nd,and Pr)from waste nickel-metal hydride(NiMH)batteries.This method does not require saponification and organic solvents.The novel phosphates,i.e.,dibenzyl phosphate(DBP),diphenyl phosphate(DPP),triphenyl phosphate(TPP)were studied as extraction-precipitants.DBP has high precipitation efficiencies for RE^(3+),which can reach 97.84%,100%,100%and 99.77%,respectively.In addition,the precipitation efficiencies of Mn^(2+),Co^(2+)and Ni^(2+)are less than 1.75%.DBP-RE has the largest particle size(D10=52.6μm,D50=135.35μm,D90=296.08μm),which is much larger than the precipitations formed by NH_(4)HCO_(3),H_(2)C2O_(4),CaO and MgO.The larger precipitation particle sizes contribute to improving the solid-liquid separation efficiency.With 3 mol/L hydrochloric acid,the stripping efficiency of DBP-RE reaches 98.60%,and the purity of recovered RE is 99.85%.The regenerated DBP can be directly used for the recycling extraction.Therefore,the novel extraction-precipitation strategy is a green and sustainable separation method.
基金financially supported by NNSFC(No.21025104,21271171,and 91022018)
文摘Hybrid materials are attracting intensive attention for their applications in electronics, photoelectronics, LEDs, field-effect transistors, etc. Engineering new hybrid materials and further exploiting their new functions will be significant for future science and technique development. In this work, alternatively stacked self-assembled CoAl LDH/MoS2 nanohybrid has been successfully synthesized by an exfoliation-flocculation method from positively charged CoAl LDH nanosheets（CoAl-NS） with negatively charged MoS2 nanosheets（MoS2-NS）. The CoAl LDH/MoS2 hybrid material exhibits an enhanced catalytic performance for oxygen evolution reaction（OER） compared with original constituents of CoAl LDH nanosheets and MoS2 nanosheets. The enhanced OER catalytic performance of CoAl LDH/MoS2 is demonstrated to be due to the improved electron transfer, more exposed catalytic active sites, and accelerated oxygen evolution reaction kinetics.
基金supported by the National Basic Research Program (973) of China (No.2010CB933501)the National Natural Science Foundation of China (No.21477128)The National Science Fund for Distinguished Young Scholars (No.21125730)
文摘Mg-A1-C1 layered double hydroxide （C1-LDH） was prepared to simultaneously remove Cu（II） and Cr（VI） from aqueous solution. The coexisting Cu（II） （20 mg/L） and Cr（VI） （40 mg/L） were completely removed within 30 min by C1-LDH in a dosage of 2.0 g/L; the removal rate of Cu（II） was accelerated in the presence of cr（VI）. Moreover, compared with the adsorption of single Cu（II） or Cr（VI）, the adsorption capacities of C1-LDH for Cu（II） and Cr（VI） can be improved by 81.05% and 49.56%, respectively, in the case of coexisting Cu（II） （200 mg/L） and Cr（VI） （400 mg/L）. The affecting factors （such as solution initial pH, adsorbent dosage, and contact time） have been systematically investigated. Besides, the changes of pH values and the concentrations of Mg2＋ and A13＋ in relevant solutions were monitored. To get the underlying mechanism, the C1-LDH samples before and after adsorption were thoroughly characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. On the basis of these analyses, a possible mechanism was proposed. The coadsorption process involves anion exchange of Cr（VI） with C1- in C1-LDH interlayer, isomorphic substitution of Mg2＋ with Cu2＋, formation of Cu2CI（OH）3 precipitation, and the adsorption of Cr（VI） by Cu2CI（OH）3. This work provides a new insight into simultaneous removal of heavy metal cations and anions from wastewater by CI-LDH.
基金supported by the National Natural Science Foundation of China(21521061,51672271,21671190)the Natural Science Foundation of Fujian Province(2006L2005)
文摘A binuclear cuprous complex [Cu（μ-I）（NPPh）]2（1,NPPh = 1-（2-（diphenylphosphanyl）phenyl）-3-phenyl-4,5-dihydro-1 H-pyrazole） was synthesized and characterized by elemental analysis,NMR and X-ray single-crystal structure analysis.It crystallizes in triclinic space group P2_1/n with a = 10.7520（3）,b = 18.1860（5）,c = 11.8487（3） ？,β = 91.864（2）,V = 2315.61（11） ？~3,Z = 4,Mr = 594.87,Dc = 1.706 g/cm^3,F（000） = 1176.0,μ = 12.582 mm（-1）,GOOF = 1.048,the final R = 0.0289 and wR = 0.0670 for 3787 observed reflections with I 〉 2σ（I）.The Cu atoms in the complex are four-coordinated and adopt distorted tetrahedral coordination geometry.In the solid state,the complex exhibits greenish yellow photoluminescence with a peak maximum of 533 nm,a decay time of 34 μs,and a photoluminescence quantum yield of 63.6% at room temperature,respectively.
基金supported by the National Natural Science Foundation of China(22171266)the FJIRSM&IUE Joint Research Fund(RHZX-2019-002)+2 种基金the STS Project(KFJ-STS-QYZD-2021-09002)the National Key Basic Research Program of China(2017YFA0403402)the Project of the National Natural Science Foundation of China(U1932119)。
文摘Fe/N/C catalysts,synthesized through the pyrolysis of Fe-doped metal–organic framework (MOF) precursors,have attracted extensive attention owing to their promising oxygen reduction reaction (ORR) catalytic activity in fuel cells and/or metal-air batteries.However,post-treatments (acid washing,second pyrolysis,and so on) are unavoidable to improve ORR catalytic activity and stability.The method for introducing Fe^(3+) sources (anhydrous Fe Cl_(3)) into the MOF structure,in particular,is a critical step that can avoid time-consuming post-treatments and result in more exposed Fe-N_(x) active sites.Herein,three different Fe doping strategies were systematically investigated to explore their influence on the types of active sites formed and ORR performance.Fe-NC(Zn^(2+)),synthesized by one-step pyrolysis of Fe doped ZIF-8 (Zn^(2+)) precursor which was obtained by adding the anhydrous Fe Cl_(3)source into the Zn(NO_(3))_(2)·6H_(2)O/methanol solution before mixing,possessed the highest Fe-N_(x)active sites due to the high-efficiency substitution of Zn^(2+)ions with Fe^(3+) ions during ZIF-8 growth,the strong interaction between Fe^(3+) ions and N atoms of 2-Methylimidazole (2-MIm),and ZIF-8’s micropore confinement effect.As a result,Fe-NC(Zn^(2+)) presented high ORR activity in the entire p H range (p H=1,7,and 13).At p H=13,Fe-NC(Zn^(2+)) exhibited a half-wave potential (E1/2) of 0.95 V (vs.reversible hydrogen electrode),which was 70 m V higher than that of commercial Pt/C.More importantly,Fe-NC(Zn^(2+)) showed superior ORR stability in neutral media without performance loss after 5,000 cycles.A record-high open-circuit voltage(1.9 V) was obtained when Fe-NC(Zn^(2+)) was used as a cathodic catalyst in assembled Mg-air batteries in neutral media.The assembled liquid and all-solid Mg-air batteries with high performance indicated that Fe-NC(Zn^(2+)) has enormous potential for use in flexible and wearable Mg-air batteries.
基金supported by the National Natural Science Foundation of China(Project No.21875253)the CAS Commonwealth Scientific and Industrial Research Organization(CSIRO)Joint Research Projects(121835KYSB20200039)+3 种基金the Scientific Research and Equipment Development Project of CAS(YJKYYQ20190007)Fujian Natural Science Foundation(2021J01210293)the Fujian Science and Technology Pilot Project(Project No.2020H0039)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(Grant.YLUDNL Fund 2021011)。
文摘Electrolytic water splitting,as a promising route to hydrogen(H_(2))production,is still confronted with the sluggish anodic oxygen evolution reaction(OER)and its less value-added O2 production.Herein,we report a bifunctional electrode fabricated by in situ growth of Mn-doped CoSe_(2)nanonetworks on carbon fiber cloth(Mn-CoSe_(2)/CFC),which shows attractive electrocatalytic properties toward glycerol oxidation reaction(GOR)in alkali and hydrogen evolution reaction(HER)in acid.A flow alkali/acid hybrid electrolytic cell(fA/A-hEC)was then developed by coupling anodic GOR with cathodic HER with the Mn-CoSe_(2)/CFC bifunctional electrode.Such fA/A-hEC enables a rather low voltage of 0.54 V to achieve 10 mA cm^(-2),and maintain long-term electrolysis stability over 300-h operation at 100 mA cm^(-2)with Faraday efficiencies of over 99%for H_(2)and 90%for formate production.The designed bifunctional electrode in such innovative fA/A-hEC device provides insightful guidance for coupling energy-efficient hydrogen production with biomass upgradation.
基金supported by the National Natural Science Foundation of China(Nos.21773247,22275185,21521061,21875252)the Natural Science Foundation of Fujian Province(No.2006L2005).
文摘Partial substitution of polyoxometalate(POM)is an efficient route to modulate the catalytic property of maternal POM.In this work,a new Keggin type POM involving{Ni 6}cluster,{[Ni(H_(2)O)_(2)(Dach)_(2)][Ni(Dach)_(2)]_(2)}{[Ni_(6)Cl(μ-OH)_(3)(H_(2)O)(Dach)_(3)(WO_(4))(PW9 O_(3)_(4))][Ni_(6)(μ-OH)_(3)(H_(2)O)_(2)(Dach)_(3)(WO_(4))(PW9 O_(3)_(4))]}Cl·27H_(2)O,(1,Dach=1,2-diaminocyclohexane)was synthesized.Compounds 1 shows excellent catalytic performance in the selective oxidation of aniline to azoxybenzene(AOB)in water.The apparently different results from that with the matrix{PW_(9)O_(34)}({PW9})suggest the successful regulation of the catalytic property of{PW9}by the introduction of the{Ni6}cluster into the skeleton.The experimental results indicate that the highlighted performance of 1 is contributed by the synergy of W and Ni sites,which are respectively responsible for the oxidation and condensation steps in the production of AOB.The good selectivity to AOB is essentially attributed to the effective modulation of the reaction rates of oxidation and condensation steps by W and Ni sites,respectively.
基金Project supported by the National Natural Science Foundation of China(11974351)。
文摘Full-spectrum phosphor-converted white-light-emitting diodes(pc-WLED)are emerging as a mainstream technology in semiconductor lighting.Nevertheless,high-performance blue phosphor which can be excited efficiently by a 400 nm NUV diode chip is still lacking.Herein,we present a blue-emitting Na_(3)KMg_(7)(PO_(4))6:Eu^(2+)phosphor synthesized by the solid-reaction method.Particularly,we find that the using of Li_(2)CO_(3)as flux can significantly improve the crystal quality and thus the emission efficiency of the phosphor.Meanwhile,the excitation peak of the phosphor shifts from 365 to 400 nm,which is pivotal for efficient NUV(400 nm)diode chip excitation.The practical Eu^(2+)concentration is also enhanced by using Li_(2)CO_(3)as flux,and the absorption efficiency is greatly increased.This phosphor exhibits superior PL thermal stability,namely retains 94%integrated photoluminescence intensity at 150℃of that at 25℃.As a result,the optimized phosphor shows an emission band peaked at 437 nm with a bandwidth of 40 nm and a high external photoluminescence quantum yield of 51.7%.Finally,a pc-WLED was fabricated by using NKMPO:Eu^(2+)blue,Sr_(2)SiO_(4):Eu^(2+)green,CaAlSiN_(3):Eu^(2+)red phosphors,and a 400 nm NUV diode chip.It shows a high color rendering index of R_(a)=96.4 and a correlated color temperature of 4358 K.These results prove that NKMPO:Eu^(2+)is a promising blue phosphor for full-spectrum WLED based on NUV diode chips.
基金supported by the National Natural Science Foundation of China(51172232)
文摘A cuprous dimer [Cu（POP）]2（pz4B）BF4·（CH3CN）3 （1, POP = bis（2-（diphenylphosphanyl）phenyl）ether, pz4B- = tetrakis（pyrazol-i-yl）borate anion） was synthesized from the reaction of Cu（CH3CN）4BF4, POP and Kpz4B in CH3CN at room temperature. The compound was characterized by elemental analysis and X-ray single-Crystal structure analysis. It crystallizes in monoclinic, space group P21/c with a = 12.3491（2）, b = 20.8845（3）, c = 33.0657（4） A, β = 94.251（1）°, V = 8504.3（2） A3, Z = 4, Mr = 1693.21, Dc = 1.322 g/cm3, F（000） = 3496,μ = 1.843 mm-1, GOOF = 1.031, the final R = 0.0442 and wR = 0.1235 for 14397 observed reflections with 1〉 2σ（I）. 1 is an ionic compound. It is composed of a BF4- anion and a {[Cu（POP）]2（pz4B）}＋ cation. The cation contains two [Cu（POP）]＋ cationic moieties and a pz4B- anionic linker. The Cu（I） ions show a distorted tetrahedral coordination geometry defined by two nitrogen atoms from a pz4B- bridging ligand and two phosphorous atoms from a POP terminal chelating ligand. The complex emits blue luminescence with the maximum peak at 457 nm with 3% quantum yield in solid state at room temperature. The Cu（I） centers are essentially electronically separated because both HOMO and LUMO contain very little contribution from the bridging ligand. The unexpected low emission is ascribed to the intramolecular interaction of the emissive centers.
基金financially supported by NSFC(No.21571176,21611530688,21771171,21671077 and 21025104)
文摘Constructing layered-spinel composites is important to improve the rate performance of lithium-rich layered oxides.However,up to now,the effect of microstructure of composites on the rate performance has not been well investigated.In this study,a series of samples were prepared by a simple protonation and de-protonation for the pristine layered material(LiMnNiCoO)obtained by sol-gel method.The characterizations of XRD,Raman and oxidation-reduction potentials of charge-discharge curves demonstrated that these samples after de-protonation are layered-spinel composites.When these composites were tested as a cathode of lithium-ion batteries,the sample treated with 0.1 M of nitric acid exhibited higher discharge capacities at each current density than that of other composites.The outstanding rate performance is attributed to the high concentration of conduction electron resulting from the low average valence state(44.2%of Ni)as confirmed by its high conductivity(1.124×10??mat39800Hz)and ambient temperature magnetic susceptibility(8.40×10emu/Oe?mol).This work has a guiding significance for the synthesis of high rate performance of lithium battery cathode materials.
基金Supported by the 1000 Plan Professorship for Young Talents,Hundred Talents Program of Fujian Provincethe Fujian Science and Technology Key Project(Item Number 2016H0043)
文摘Using the bottom-up method, we synthesized a series of perfluorinated covalent triazine-based frameworks(FCTFs) with porous structures for catalysis oxygen reduction reaction(ORR). The evolved FCTFs by high-temperature carbonization show an apparent variation in electrocatalytic activity toward the ORR dependent on the type of F. The samples synthesized at 900 ℃(FCTF-900) exhibits advantages in terms of high activity, high durability, and methanol-tolerant as an efficient electrocatalyst for ORR, manifests a comparable or even better activity as compared with the commercial Pt/C catalysts not only in alkaline media but also in acidic and neutral electrolyte.
基金financially supported by the National Natural Science Foundation of China(Project No.21875253,No.51903235)。
文摘Electrosynthesis has recently attracted intensive research attentions and holds great potential in implementing scalable green synthesis thanks to more and more readily accessible renewable electric energy.
基金supported by National Science Foundation for Youths of China(Nos.22209184 and 22109163)。
文摘The detrimental“shuttle effect”of lithium polysulfides(LiPSs)together with sluggish multi-order reaction kinetics are the main drawbacks hindering lithium-sulfur(Li-S)batteries from commercial success.Here,we first propose the implementability of layered rare-earth hydroxides(LREHs)in Li-S batteries to optimize electrochemical performance.In this work,a two-dimensional(2D)rare-earth-based composite constructed by the layered gadolinium hydroxy chloride[Gd_(2)(OH)_(5)(H_(2)O)_(n)]Cl nanoplates(LGdH NPs)and graphene oxide(GO)was designed as a sulfur immobilizer for Li-S batteries.Combining the experimental results and density functional theory(DFT)calculations,it is revealed that the LGdH@GO composite not only provides a strong anchoring of the intermediates during cycling,but also acts as an effective catalyst to accelerate the liquid-solid conversion of polysulfides.The Li-S batteries assembled by LGdH@GO modified separators delivered a superior rate performance with a specific capacity of 605.34 mAh/g at 5 C,as well as excellent cycle stability with a decay rate of 0.087%over 500 cycles at 2 C.This study provided a deep understanding of the mechanism to suppress the“shuttle effect”by the LREHs,and a guide to design effective functional interlayers for high-performance Li-S batteries with excellent electrocatalytic activity.
