Lithium-sulfur(Li-S)batteries have attracted wide attention for their high theoretical energy density,low cost,and environmental friendliness.However,the shuttle effect of polysulfides and the insulation of active mat...Lithium-sulfur(Li-S)batteries have attracted wide attention for their high theoretical energy density,low cost,and environmental friendliness.However,the shuttle effect of polysulfides and the insulation of active materials severely restrict the development of Li-S batteries.Constructing conductive sulfur scaffolds with catalytic conversion capability for cathodes is an efficient approach to solving above issues.Vanadium-based compounds and their heterostructures have recently emerged as functional sulfur catalysts supported on conductive scaffolds.These compounds interact with polysulfides via different mechanisms to alleviate the shuttle effect and accelerate the redox kinetics,leading to higher Coulombic efficiency and enhanced sulfur utilization.Reports on vanadium-based nanomaterials in Li-S batteries have been steadily increasing over the past several years.In this review,first,we provide an overview of the synthesis of vanadium-based compounds and heterostructures.Then,we discuss the interactions and constitutive relationships between vanadium-based catalysts and polysulfides formed at sulfur cathodes.We summarize the mechanisms that contribute to the enhancement of electrochemical performance for various types of vanadium-based catalysts,thus providing insights for the rational design of sulfur catalysts.Finally,we offer a perspective on the future directions for the research and development of vanadium-based sulfur catalysts.展开更多
Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membr...Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.展开更多
Iron is an impurity widely occurred in sphalerite,and its effect on sphalerite flotation is complex.In this work,the effects of iron content and spin state on electronic properties and floatability of iron-bearing sph...Iron is an impurity widely occurred in sphalerite,and its effect on sphalerite flotation is complex.In this work,the effects of iron content and spin state on electronic properties and floatability of iron-bearing sphalerite are comprehensively studied using density functional theory Hubbard U(DFT+U)calculations combined with coordination chemistry flotation.The band gap of ideal sphalerite is 3.723 eV,and thus electron transition is difficult to occur,resulting in poor floatability.The results suggest the band gap of sphalerite decreases with increasing iron content.For low iron content,the decreased band gap facilitates electron transition;at this case,Fe^(2+)in a high-spin state possesses oneπelectron pair,which can form a weakπ-backbonding with xanthate,causing increasing floatability.However,for medium and high iron-bearing sphalerite,with the further decrease of band gap,Fe^(2+)is oxidized to Fe^(3+)due to electrochemical interaction,and henceπ-backbonding is eliminated,leading to lower floatability of iron-bearing sphalerite,which is consistent with the flotation experimental results.This work could give a deeper understanding of how sphalerite flotation behaviors are affected by iron content.展开更多
Mechanical excavation,blasting,adjacent rockburst and fracture slip that occur during mining excavation impose dynamic loads on the rock mass,leading to further fracture of damaged surrounding rock in three-dimensiona...Mechanical excavation,blasting,adjacent rockburst and fracture slip that occur during mining excavation impose dynamic loads on the rock mass,leading to further fracture of damaged surrounding rock in three-dimensional high-stress and even causing disasters.Therefore,a novel complex true triaxial static-dynamic combined loading method reflecting underground excavation damage and then frequent intermittent disturbance failure is proposed.True triaxial static compression and intermittent disturbance tests are carried out on monzogabbro.The effects of intermediate principal stress and amplitude on the strength characteristics,deformation characteristics,failure characteristics,and precursors of monzogabbro are analyzed,intermediate principal stress and amplitude increase monzogabbro strength and tensile fracture mechanism.Rapid increases in microseismic parameters during rock loading can be precursors for intermittent rock disturbance.Based on the experimental result,the new damage fractional elements and method with considering crack initiation stress and crack unstable stress as initiation and acceleration condition of intermittent disturbance irreversible deformation are proposed.A novel three-dimensional disturbance fractional deterioration model considering the intermediate principal stress effect and intermittent disturbance damage effect is established,and the model predicted results align well with the experimental results.The sensitivity of stress states and model parameters is further explored,and the intermittent disturbance behaviors at different f are predicted.This study provides valuable theoretical bases for the stability analysis of deep mining engineering under dynamic loads.展开更多
With the application of resins in various fields, numerous waste resins that are difficult to treat have been produced. The industrial wastewater containing Cr(Ⅵ) has severely polluted soil and groundwater environmen...With the application of resins in various fields, numerous waste resins that are difficult to treat have been produced. The industrial wastewater containing Cr(Ⅵ) has severely polluted soil and groundwater environments, thereby endangering human health. Therefore, in this paper, a novel functionalized mesoporous adsorbent PPR-Z was synthesized from waste amidoxime resin for adsorbing Cr(Ⅵ). The waste amidoxime resin was first modified with H3PO4 and ZnCl_(2), and subsequently, it was carbonized through slow thermal decomposition. The static adsorption of PPR-Z conforms to the pseudo-second-order kinetic model and Langmuir isotherm, indicating that the Cr(Ⅵ) adsorption by PPR-Z is mostly chemical adsorption and exhibits single-layer adsorption. The saturated adsorption capacity of the adsorbent for Cr(Ⅵ) could reach 255.86 mg/g. The adsorbent could effectively reduce Cr(Ⅵ) to Cr(Ⅲ) and decrease the toxicity of Cr(Ⅵ) during adsorption. PPR-Z exhibited Cr(Ⅵ) selectivity in electroplating wastewater. The main mechanisms involved in the Cr(Ⅵ) adsorption are the chemical reduction of Cr(Ⅵ) into Cr(Ⅲ) and electrostatic and coordination interactions. Preparation of PPR-Z not only solves the problem of waste resin treatment but also effectively controls Cr(Ⅵ) pollution and realizes the concept of “treating waste with waste”.展开更多
Sb_(2)Se_(3) with unique one-dimensional(1D) crystal structure exhibits exceptional deformation tolerance,demonstrating great application potential in flexible devices.However,the power conversion efficiency(PCE) of f...Sb_(2)Se_(3) with unique one-dimensional(1D) crystal structure exhibits exceptional deformation tolerance,demonstrating great application potential in flexible devices.However,the power conversion efficiency(PCE) of flexible Sb_(2)Se_(3) photovoltaic devices is temporarily limited by the complicated intrinsic defects and the undesirable contact interfaces.Herein,a high-quality Sb_(2)Se_(3) absorber layer with large crystal grains and benign [hkl] growth orientation can be first prepared on a Mo foil substrate.Then NaF intermediate layer is introduced between Mo and Sb_(2)Se_(3),which can further optimize the growth of Sb_(2)Se_(3)thin film.Moreover,positive Na ion diffusion enables it to dramatically lower barrier height at the back contact interface and passivate harmful defects at both bulk and heterojunction.As a result,the champion substrate structured Mo-foil/Mo/NaF/Sb_(2)Se_(3)/CdS/ITO/Ag flexible thin-film solar cell delivers an obviously higher efficiency of 8.03% and a record open-circuit voltage(V_(OC)) of 0.492 V.This flexible Sb_(2)Se_(3) device also exhibits excellent stability and flexibility to stand large bending radius and multiple bending times,as well as superior weak light photo-response with derived efficiency of 12.60%.This work presents an effective strategy to enhance the flexible Sb_(2)Se_(3) device performance and expand its potential photovoltaic applications.展开更多
Recently,many lead-free metal halides with diverse structures and highly efficient emission have been reported.However,their poor stability and single-mode emission color severely limit their applications.Herein,three...Recently,many lead-free metal halides with diverse structures and highly efficient emission have been reported.However,their poor stability and single-mode emission color severely limit their applications.Herein,three homologous Sb^(3+)-doped zero-dimensional(0D)air-stable Sn(IV)-based metal halides with different crystal structures were developed by inserting a single organic ligand into SnCl_(4)lattice,which brings different optical properties.Under photoexcitation,(C_(25)H_(22)P)SnC_(l5)@Sb⋅CH_(4O)(Sb^(3+)−1)does not emit light,(C_(25)H_(22)P)_(2)SnC_(l6)@Sb-α(Sb^(3+)−2α)shines bright yellow emission with a photoluminescence quantum yield(PLQY)of 92%,and(C_(25)H_(22)P)_(2)SnC_(l6)@Sb-β(Sb^(3+)−2β)exhibits intense red emission with a PLQY of 78%.The above three compounds show quite different optical properties should be due to their different crystal structures and the lattice distortions.Particularly,Sb^(3+)−1 can be successfully converted into Sb^(3+)−2αunder the treatment of C_(25)H_(22)PCl solution,accompanied by a transition from nonemission to efficient yellow emission,serving as a“turn-on”photoluminescence(PL)switching.Parallelly,a reversible structure conversion between Sb^(3+)−2αand Sb^(3+)−2βwas witnessed after dichloromethane or volatilization treatment,accompanied by yellow and red emission switching.Thereby,a triple-mode tunable PL switching of off-onI-onII can be constructed in Sb^(3+)-doped Sn(IV)-based compounds.Finally,we demonstrated the as-synthesized compounds in fluorescent anticounterfeiting,information encryption,and optical logic gates.展开更多
The organic carbon source coating LiFe_(x)Mn_(1-x)PO_(4)suffers from the problem of non-uniform carbon cladding.Too thick carbon cladding layer instead hinders the de-embedding of lithium ions.In this paper,we choose ...The organic carbon source coating LiFe_(x)Mn_(1-x)PO_(4)suffers from the problem of non-uniform carbon cladding.Too thick carbon cladding layer instead hinders the de-embedding of lithium ions.In this paper,we choose cornstalk as the carbon source,then LiFe_(0.5)Mn_(0.5)PO_(4)@cornstalk-C(LFMP@C-C)with 3D anchoring structure is prepared by the solvothermal method.The results show that the LFMP with cornstalk as the carbon source has better performance compared to the sucrose-coated LFMP material(LFMP@C).The discharge capacity of LFMP@C-C is 116 mAh/g for the first cycle at 1 C and the capacity retention rate is 94.0%after 500 cycles,and the discharge capacity of LFMP@C-C is more than 17.17%higher than that of LFMP@C.展开更多
As an ideal carbon-free energy carrier,ammonia plays an indispensable role in modern society.The conventional industrial synthesis of NH3 by the Haber-Bosch technique under harsh reaction conditions results in serious...As an ideal carbon-free energy carrier,ammonia plays an indispensable role in modern society.The conventional industrial synthesis of NH3 by the Haber-Bosch technique under harsh reaction conditions results in serious energy consumption and environmental pollution.Therefore,it is essential to develop NH3 synthesis tactics under benign conditions.Electrochemical synthesis of NH_(3) has the advantages of mild reaction conditions and environmental friendliness,and has become a hotspot for research in recent years.It has been reported that zinc-nitrogen batteries(ZNBs),such as Zn-N_(2),Zn-NO,Zn-NO_(3)^(-),and Zn-NO_(2)^(-)batteries,can not only reduce nitrogenous species to ammonia but also have concomitant power output.However,the common drawbacks of these battery systems are unsatisfactory power density and ammonia production.In this review,the latest progress of ZNBs including the reaction mechanism of the battery and reactor design principles is systematically summarized.Subsequently,active site engineering of cathode catalysts is discussed,including vacancy defects,chemical doping,and heterostructure engineering.Finally,some insights are provided to improve the performance of ZNBs from a practical perspective of view.展开更多
Magnesium hydride(MgH_(2))is the most feasible and effective solid-state hydrogen storage material,which has excellent reversibility but initiates decomposing at high temperatures and has slow kinetics performance.Her...Magnesium hydride(MgH_(2))is the most feasible and effective solid-state hydrogen storage material,which has excellent reversibility but initiates decomposing at high temperatures and has slow kinetics performance.Here,zinc titanate(Zn_(2)TiO_(4))synthesised by the solid-state method was used as an additive to lower the initial temperature for dehydrogenation and enhance the re/dehydrogenation behaviour of MgH_(2).With the presence of Zn_(2)TiO_(4),the starting temperature for the dehydrogenation of MgH_(2)was remarkably lowered to around 290℃–305℃.In addition,within 300 s,the MgH_(2)–Zn_(2)TiO_(4)sample absorbed 5.0 wt.%of H_(2)and 2.2–3.6 wt.%H_(2)was liberated from the composite sample in 30 min,which is faster by 22–36 times than as-milled MgH_(2).The activation energy of the MgH_(2)for the dehydrogenation process was also downshifted to 105.5 k J/mol with the addition of Zn_(2)TiO_(4)indicating a decrease of 22%than as-milled MgH_(2).The superior behaviour of MgH_(2)was due to the formation of Mg Zn_(2),MgO and MgTiO_(3),which are responsible for ameliorating the re/dehydrogenation behaviour of MgH_(2).These findings provide a new understanding of the hydrogen storage behaviour of the catalysed-MgH_(2)system.展开更多
To improve the soil and water stability of expansive soil slopes and reduce the probability of slope failure,novel protection systems based on polymer waterproof coatings(PWC)were used in this study.Herein,three group...To improve the soil and water stability of expansive soil slopes and reduce the probability of slope failure,novel protection systems based on polymer waterproof coatings(PWC)were used in this study.Herein,three groups of expansive soil slope model tests were designed to investigate the effects of polyester nonwovens and PWC(P-PWC)composite protection system,three-dimensional vegetation network and PWC(T-PWC)composite protection system,and nonprotection on the soil and water behavior in the slopes under precipitation–evaporation cycles.The results showed that the moisture change of P-PWC and T-PWC composite protected slopes was significantly smaller than that of bare slope,which reduced the sensitivity of slope moisture to environmental changes and improved its stability.The soil temperature of the slope protected by the P-PWC and T-PWC systems at a depth of 70 cm increased by 5.6℃ and 2.7℃,respectively.Using PWC composite protection systems exhibited better thermal storage performance,which could increase the utilization of shallow geothermal resources.Moreover,the maximum average crack widths of the bare slopes were 7.89 and 3.17 times those of the P-PWC and TPWC protected slopes,respectively,and the maximum average crack depths were 6.87 and 3 times those of the P-PWC and T-PWC protected slopes,separately.The PPWC protection system weakened the influence of hydro–thermal coupling on the slopes,inhibited the development of cracks on the slopes,and reduced the soil erosion.The maximum soil erosion of slopes protected by P-PWC and T-PWC systems was 332 and 164 times lower than that of bare slope,respectively.The P-PWC and T-PWC protection systems achieved excellent"anti-seepage and moisture retention"and anti-erosion effects,thus improving the soil and water stability of slopes.These findings can provide important guiding reference for controlling rainwater infiltration and soil erosion in expansive soil slope projects.展开更多
A series of single-phase double perovskite Pr1-xGdxBaCo_(2)-yFeyO_(5+σ)(x=0,0.5 and 1,0≤y≤1)materials were engineered through A/B site co-doping strategy to improve the mechanical,electrical and electrochemical pro...A series of single-phase double perovskite Pr1-xGdxBaCo_(2)-yFeyO_(5+σ)(x=0,0.5 and 1,0≤y≤1)materials were engineered through A/B site co-doping strategy to improve the mechanical,electrical and electrochemical properties as potential cathode materials for the application of intermediate solid oxide fuel cells(IT-SOFCs).The corresponding thermochemical stability,thermal expansion behavior,electrical conductivity and cathodic polarization resistance of the materials were systematically investigated.It was found that the A-site dual lanthanide doped Pr_(0.5)Gd_(0.5)BaCo_(2)O_(5+σ)(PGBCO)exhibits improved electrical conductivity,reduced thermal expansion,and comparatively low electrochemical polarization resistance versus single lanthanide double perovskite,PrBaCo_(2)O_(5+σ)(PBCO)and GdBaCo_(2)O_(5+σ)(GBCO)materials.Further investigation on the effect of B-site Fe-doping on Pr_(0.5)Gd_(0.5)BaCo_(2)-yFeyO_(5)+σ(PGBCF-y,0≤y≤1)reveals that all the PGBCF-y compositions exhibit excellent chemical stability with Gd-doped ceria(GDC)at operating temperatures not higher than 1100℃.Besides,doping of Fe in B-site can effectively reduce the thermal expansion coefficients(TECs)of the Pr_(0.5)Gd_(0.5)BaCo_(2)O_(5)+σceramics at 30e1000℃.And the electrochemical impedance spectra(EIS)results show that the PGBCF-y|GDC|PGBCF-y symmetric cells have acceptable low area specific polarization resistances.Further examination of the cathodic polarization and characteristic capacitance from the AC impedance spectra by employing the relaxation time distribution(DRT)method demonstrated that charge transfer is the dominating subprocess for the oxygen transport through the materials.展开更多
SiGe is recognised as an excellent thermoelectric material with superior mechanical properties and thermal stability in regions with high temperatures.This study explores a novel strategy for coregulating thermoelectr...SiGe is recognised as an excellent thermoelectric material with superior mechanical properties and thermal stability in regions with high temperatures.This study explores a novel strategy for coregulating thermoelectric transport parameters to achieve high thermoelectric properties of p-type SiGe in the mid-temperature region by incorporating nano-TaC into SiGe combined ball milling with spark plasma sintering.By optimizing the amount of TaC in the SiGe matrix,the power factors were significantly increased due to the modulation doping effect based on the work function matching of SiGe with TaC.Simultaneously,the ensemble effect of the nanostructure leads to a significant decrease in thermal conductivity.Thus,a high ZT of 1.06 was accomplished at 873 K,which is 64%higher than that of typical radioisotope thermoelectric generator.Our research offers a novel strategy for expanding and enhancing the thermoelectric properties of SiGe materials in the medium temperature range.展开更多
Layered double hydroxides have demonstrated great potential for the oxygen evolution reaction,which is a crucial half-reaction of overall water splitting.However,it remains challenging to apply layered double hydroxid...Layered double hydroxides have demonstrated great potential for the oxygen evolution reaction,which is a crucial half-reaction of overall water splitting.However,it remains challenging to apply layered double hydroxides in other electrochemical reactions with high efficiency and stability.Herein,we report two-dimensional multifunctional layered double hydroxides derived from metalorganic framework sheet precursors supported by nanoporous gold with high porosity,which exhibit appealing performances toward oxygen/hydrogen evolution reactions,hydrazine oxidation reaction,and overall hydrazine splitting.The as-prepared catalyst only requires an overpotential of 233 mV to reach 10 mA·cm^(-2) toward oxygen evolution reaction.The overall hydrazine splitting cell only needs a cell voltage of 0.984 V to deliver 10 mA·cm^(-2),which is far more superior than that of the overall water splitting system(1.849 V).The appealing performances of the catalyst can be contributed to the synergistic effect between the metal components of the layered double hydroxides and the supporting effect of the nanoporous gold substrate,which could endow the sample with high surface area and excellent conductivity,resulting in superior activity and stability.展开更多
Electrocatalytic nitrate reduction reaction(NO_(3)RR)offers a unique rationale for green NH_(3) synthesis,yet the lack of high-efficiency NO_(3)RR catalysts remains a great challenge.In this work,we show that Au nanoc...Electrocatalytic nitrate reduction reaction(NO_(3)RR)offers a unique rationale for green NH_(3) synthesis,yet the lack of high-efficiency NO_(3)RR catalysts remains a great challenge.In this work,we show that Au nanoclusters anchored on TiO_(2) nanosheets can efficiently catalyze the conversion of NO_(3)RR-to-NH_(3) under ambient conditions,achieving a maximal Faradic efficiency of 91%,a peak yield rate of 1923μg·h^(-1)·mgcat.-1,and high durability over 10 consecutive cycles,all of which are comparable to the recently reported metrics(including transition metal and noble metal-based catalysts)and exceed those of pristine TiO_(2).Moreover,a galvanic Zn-nitrate battery using the catalyst as the cathode was proposed,which shows a power density of 3.62 mW·cm^(-2) and a yield rate of 452μg·h^(-1)·mgcat.-1.Theoretical simulations further indicate that the atomically dispersed Au clusters can promote the adsorption and activation of NO_(3)-species,and reduce the NO_(3)RR-to-NH_(3) barrier,thus leading to an accelerated cathodic reaction.This work highlights the importance of metal clusters for the NH_(3) electrosynthesis and nitrate removal.展开更多
To improve the strength-toughness of 13Cr4NiMo martensitic stainless steel(13-4MSS),a thermal cyclic heat treatment(TCHT)combined with the advantage of tempering was proposed.The microstructures were characterized by ...To improve the strength-toughness of 13Cr4NiMo martensitic stainless steel(13-4MSS),a thermal cyclic heat treatment(TCHT)combined with the advantage of tempering was proposed.The microstructures were characterized by scanning electron microscopy,X-ray diffraction and electron backscattered diffraction,and the mechanical behaviors in terms of tensile properties and impact toughness were analyzed in correlation with microstructural evolution.It was found that grains and the martensitic matrix were refined by TCHT through the cyclic quenching transformation and austenite recrystallization,which was conducive to more nucleation quantity of reversed austenite during tempering.Two-sphericalcap nucleation model was used to explain the effect of refined grains of TCHT on the nucleation of reversed austenite.Grain refinement by TCHT improved the brittle fracture stress to reduce the ductile-brittle transition temperature and thus improved the cryogenic impact toughness of 13-4MSS.Reversed austenite distributed at the martensitic lath boundary enhances the crack arrest performance and increases the britle fracture stress.It is concluded that reasonable TCHT plus tempering process significantly improves the strength-toughness of 13-4MSS,reflecting the comprehensive effect of grain refinement and reversed austenite.展开更多
The combination of high-voltage windows and bending stability remains a challenge for supercapacitors.Here,we present an“advantage-complementary strategy”using sodium lignosulfonate as a pseudocapacitive molecule to...The combination of high-voltage windows and bending stability remains a challenge for supercapacitors.Here,we present an“advantage-complementary strategy”using sodium lignosulfonate as a pseudocapacitive molecule to regulate the spatial stacking pattern of graphene oxide and the interfacial architectures of graphene oxide and polyaniline.Flexible and sustainable sodium lignosulfonate-based electrodes are successfully developed,showing perfect bending stability and high electronic conductivity and specific capacitance(521 F·g^(−1)at 0.5 A·g^(−1)).Due to the resulting rational interfacial structure and stable ion-electron transport,the asymmetric supercapacitors provide a wide voltage window reaching 1.7 V,outstanding bending stability and high energy-power density of 83.87 Wh·kg^(−1)at 3.4 kW·kg^(−1).These properties are superior to other reported cases of asymmetric energy enrichment.The synergistic strategy of sodium lignosulfonate on graphene oxide and polyaniline is undoubtedly beneficial to advance the process for the construction of green flexible supercapacitors with remarkably wide voltage windows and excellent bending stability.展开更多
Facilitated by reactive oxygen species(ROS)-involved therapies,tumor cells undergo immunogenic cell death(ICD)to stimulate long-term immunity response.However,it is hard to trigger abundant and large-scale ICD for sat...Facilitated by reactive oxygen species(ROS)-involved therapies,tumor cells undergo immunogenic cell death(ICD)to stimulate long-term immunity response.However,it is hard to trigger abundant and large-scale ICD for satisfactory cancer immunotherapy.Herein,a multifunctional sonosensitizer that consists of Au single atoms and clusters anchored on TiO_(2)nanosheets(named Au_(S/C)-TiO_(2))is reported for augmented sonodynamic therapy(SDT)and glucose depletion,which ultimately induce robust ICD due to the improved ROS generation and strong endoplasmic reticulum(ER)stress.The synergy effect between Au cluster/single atom with TiO_(2)nanosheets intensifies apoptosis and ICD pathways to inhibit 80%of tumor cells through in vivo analyses.Furthermore,immune cells in vivo analyses verify the effectiveness of Au_(S/C)-TiO_(2)sonosensitizer towards the induction of antitumor immunity.This study thus reveals that simultaneous presence of ROS generation and strong ER stress can efficiently evoke a strong ICD-mediated immune response.展开更多
Sb-based organic–inorganic hybrid metal halides(OIHMHs)with[SbCl5]2−units have been widely reported due to high photoluminescence quantum yield(PLQY)and occasional multiple self-trapped exciton(STE)emission bands mai...Sb-based organic–inorganic hybrid metal halides(OIHMHs)with[SbCl5]2−units have been widely reported due to high photoluminescence quantum yield(PLQY)and occasional multiple self-trapped exciton(STE)emission bands mainly out of singlet and triplet states,and their multi-band emission is important in white light-emitting diode(WLED).However,not all these OIHMH compounds can produce both emissions out of singlet STE and triplet STE at room temperature simultaneously.It is crucial to consider how the singlet STE generates and retains to emit light at room temperature for this material’s design and application.Herein,a strategy is proposed that can significantly lift Sb halide PLQY by synthesizing two Sb-based OIHMHs using organic amine cations of different-sized and-quantity,which modulate the distance of neighboring emission centers.Therein,the occurrence of singlet STE emission is found to be closely related to the distance of[SbCl_(5)]^(2)−units and local unit distortion in the lattice.The larger distance can produce smaller local distortions,favoring the formation of the singlet STE emission band at higher energy.This is the first work to reveal the relationship between the local structure and the origin of the singlet STE emission band,providing new insights into the modulation of the Sb-based OIHMH’s emission.展开更多
基金supported by the National Natural Science Foundation of China(51962002)the Natural Science Foundation of Guangxi(2022GXNSFAA035463)the National Key R&D Program of China(2022YFB2404402)。
文摘Lithium-sulfur(Li-S)batteries have attracted wide attention for their high theoretical energy density,low cost,and environmental friendliness.However,the shuttle effect of polysulfides and the insulation of active materials severely restrict the development of Li-S batteries.Constructing conductive sulfur scaffolds with catalytic conversion capability for cathodes is an efficient approach to solving above issues.Vanadium-based compounds and their heterostructures have recently emerged as functional sulfur catalysts supported on conductive scaffolds.These compounds interact with polysulfides via different mechanisms to alleviate the shuttle effect and accelerate the redox kinetics,leading to higher Coulombic efficiency and enhanced sulfur utilization.Reports on vanadium-based nanomaterials in Li-S batteries have been steadily increasing over the past several years.In this review,first,we provide an overview of the synthesis of vanadium-based compounds and heterostructures.Then,we discuss the interactions and constitutive relationships between vanadium-based catalysts and polysulfides formed at sulfur cathodes.We summarize the mechanisms that contribute to the enhancement of electrochemical performance for various types of vanadium-based catalysts,thus providing insights for the rational design of sulfur catalysts.Finally,we offer a perspective on the future directions for the research and development of vanadium-based sulfur catalysts.
基金finically supported by the National Natural Science Foundation of China(22075055)the Guangxi Science and Technology Project(AB16380030)。
文摘Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.
基金This work was supported by the National Natural Science Foundation of People’s Republic of China(No.NSFC52174246)the Interdisciplinary Scientific Research Foundation of Guangxi University(No.2022JCC016).
文摘Iron is an impurity widely occurred in sphalerite,and its effect on sphalerite flotation is complex.In this work,the effects of iron content and spin state on electronic properties and floatability of iron-bearing sphalerite are comprehensively studied using density functional theory Hubbard U(DFT+U)calculations combined with coordination chemistry flotation.The band gap of ideal sphalerite is 3.723 eV,and thus electron transition is difficult to occur,resulting in poor floatability.The results suggest the band gap of sphalerite decreases with increasing iron content.For low iron content,the decreased band gap facilitates electron transition;at this case,Fe^(2+)in a high-spin state possesses oneπelectron pair,which can form a weakπ-backbonding with xanthate,causing increasing floatability.However,for medium and high iron-bearing sphalerite,with the further decrease of band gap,Fe^(2+)is oxidized to Fe^(3+)due to electrochemical interaction,and henceπ-backbonding is eliminated,leading to lower floatability of iron-bearing sphalerite,which is consistent with the flotation experimental results.This work could give a deeper understanding of how sphalerite flotation behaviors are affected by iron content.
基金the financial support from the National Natural Science Foundation of China(No.52109119)the Guangxi Natural Science Foundation(No.2021GXNSFBA075030)+2 种基金the Guangxi Science and Technology Project(No.Guike AD20325002)the Chinese Postdoctoral Science Fund Project(No.2022 M723408)the Open Research Fund of State Key Laboratory of Simulation and Regulation of Water Cycle in River Basin(China Institute of Water Resources and Hydropower Research)(No.IWHR-SKL-202202).
文摘Mechanical excavation,blasting,adjacent rockburst and fracture slip that occur during mining excavation impose dynamic loads on the rock mass,leading to further fracture of damaged surrounding rock in three-dimensional high-stress and even causing disasters.Therefore,a novel complex true triaxial static-dynamic combined loading method reflecting underground excavation damage and then frequent intermittent disturbance failure is proposed.True triaxial static compression and intermittent disturbance tests are carried out on monzogabbro.The effects of intermediate principal stress and amplitude on the strength characteristics,deformation characteristics,failure characteristics,and precursors of monzogabbro are analyzed,intermediate principal stress and amplitude increase monzogabbro strength and tensile fracture mechanism.Rapid increases in microseismic parameters during rock loading can be precursors for intermittent rock disturbance.Based on the experimental result,the new damage fractional elements and method with considering crack initiation stress and crack unstable stress as initiation and acceleration condition of intermittent disturbance irreversible deformation are proposed.A novel three-dimensional disturbance fractional deterioration model considering the intermediate principal stress effect and intermittent disturbance damage effect is established,and the model predicted results align well with the experimental results.The sensitivity of stress states and model parameters is further explored,and the intermittent disturbance behaviors at different f are predicted.This study provides valuable theoretical bases for the stability analysis of deep mining engineering under dynamic loads.
基金supported by the National Natural Science Foundation of China (No.52364022)the Natural Science Foundation of Guangxi Province,China (Nos.2023JJA160192 and 2021GXNSFAA220096)+1 种基金the Guangxi Science and Technology Major Project,China (No.AA23073018)the Guangxi Chongzuo Science and Technology Plan,China (No.2023ZY00503).
文摘With the application of resins in various fields, numerous waste resins that are difficult to treat have been produced. The industrial wastewater containing Cr(Ⅵ) has severely polluted soil and groundwater environments, thereby endangering human health. Therefore, in this paper, a novel functionalized mesoporous adsorbent PPR-Z was synthesized from waste amidoxime resin for adsorbing Cr(Ⅵ). The waste amidoxime resin was first modified with H3PO4 and ZnCl_(2), and subsequently, it was carbonized through slow thermal decomposition. The static adsorption of PPR-Z conforms to the pseudo-second-order kinetic model and Langmuir isotherm, indicating that the Cr(Ⅵ) adsorption by PPR-Z is mostly chemical adsorption and exhibits single-layer adsorption. The saturated adsorption capacity of the adsorbent for Cr(Ⅵ) could reach 255.86 mg/g. The adsorbent could effectively reduce Cr(Ⅵ) to Cr(Ⅲ) and decrease the toxicity of Cr(Ⅵ) during adsorption. PPR-Z exhibited Cr(Ⅵ) selectivity in electroplating wastewater. The main mechanisms involved in the Cr(Ⅵ) adsorption are the chemical reduction of Cr(Ⅵ) into Cr(Ⅲ) and electrostatic and coordination interactions. Preparation of PPR-Z not only solves the problem of waste resin treatment but also effectively controls Cr(Ⅵ) pollution and realizes the concept of “treating waste with waste”.
基金supported by the National Natural Science Foundation of China(Grant Nos.62104156,62074102)the Guangdong Basic and Applied Basic Research Foundation(Grant Nos.2023A1515011256,2022A1515010979)China+1 种基金Science and Technology plan project of Shenzhen(Grant Nos.20220808165025003,20200812000347001)Chinasupported by the open foundation of Guangxi Key Laboratory of Processing for Non-ferrous Metals and Featured Materials,State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures,Guangxi University(Grant No.2022GXYSOF13)。
文摘Sb_(2)Se_(3) with unique one-dimensional(1D) crystal structure exhibits exceptional deformation tolerance,demonstrating great application potential in flexible devices.However,the power conversion efficiency(PCE) of flexible Sb_(2)Se_(3) photovoltaic devices is temporarily limited by the complicated intrinsic defects and the undesirable contact interfaces.Herein,a high-quality Sb_(2)Se_(3) absorber layer with large crystal grains and benign [hkl] growth orientation can be first prepared on a Mo foil substrate.Then NaF intermediate layer is introduced between Mo and Sb_(2)Se_(3),which can further optimize the growth of Sb_(2)Se_(3)thin film.Moreover,positive Na ion diffusion enables it to dramatically lower barrier height at the back contact interface and passivate harmful defects at both bulk and heterojunction.As a result,the champion substrate structured Mo-foil/Mo/NaF/Sb_(2)Se_(3)/CdS/ITO/Ag flexible thin-film solar cell delivers an obviously higher efficiency of 8.03% and a record open-circuit voltage(V_(OC)) of 0.492 V.This flexible Sb_(2)Se_(3) device also exhibits excellent stability and flexibility to stand large bending radius and multiple bending times,as well as superior weak light photo-response with derived efficiency of 12.60%.This work presents an effective strategy to enhance the flexible Sb_(2)Se_(3) device performance and expand its potential photovoltaic applications.
基金Guangxi Graduate Education,Grant/Award Number:YCSW2023026Scientific and Technological Bases and Talents of Guangxi,Grant/Award Numbers:AD23026119,AD21238027Guangxi NSF project,Grant/Award Number:2020GXNSFDA238004。
文摘Recently,many lead-free metal halides with diverse structures and highly efficient emission have been reported.However,their poor stability and single-mode emission color severely limit their applications.Herein,three homologous Sb^(3+)-doped zero-dimensional(0D)air-stable Sn(IV)-based metal halides with different crystal structures were developed by inserting a single organic ligand into SnCl_(4)lattice,which brings different optical properties.Under photoexcitation,(C_(25)H_(22)P)SnC_(l5)@Sb⋅CH_(4O)(Sb^(3+)−1)does not emit light,(C_(25)H_(22)P)_(2)SnC_(l6)@Sb-α(Sb^(3+)−2α)shines bright yellow emission with a photoluminescence quantum yield(PLQY)of 92%,and(C_(25)H_(22)P)_(2)SnC_(l6)@Sb-β(Sb^(3+)−2β)exhibits intense red emission with a PLQY of 78%.The above three compounds show quite different optical properties should be due to their different crystal structures and the lattice distortions.Particularly,Sb^(3+)−1 can be successfully converted into Sb^(3+)−2αunder the treatment of C_(25)H_(22)PCl solution,accompanied by a transition from nonemission to efficient yellow emission,serving as a“turn-on”photoluminescence(PL)switching.Parallelly,a reversible structure conversion between Sb^(3+)−2αand Sb^(3+)−2βwas witnessed after dichloromethane or volatilization treatment,accompanied by yellow and red emission switching.Thereby,a triple-mode tunable PL switching of off-onI-onII can be constructed in Sb^(3+)-doped Sn(IV)-based compounds.Finally,we demonstrated the as-synthesized compounds in fluorescent anticounterfeiting,information encryption,and optical logic gates.
基金supported by CITIC Dameng Mining Industries Limited-Guangxi University Joint Research Institute of manganese resources utilization and advanced materials technology,Guangxi University-CITIC Dameng Mining Industries Limited Joint base of postgraduate cultivation,National Natural Science Foundation of China(No.11364003)Guangxi Innovation Driven Development Project(Nos.AA17204100,AA18118052)the Natural Science Foundation of Guangxi Province(No.2018GXNSFAA138186)。
文摘The organic carbon source coating LiFe_(x)Mn_(1-x)PO_(4)suffers from the problem of non-uniform carbon cladding.Too thick carbon cladding layer instead hinders the de-embedding of lithium ions.In this paper,we choose cornstalk as the carbon source,then LiFe_(0.5)Mn_(0.5)PO_(4)@cornstalk-C(LFMP@C-C)with 3D anchoring structure is prepared by the solvothermal method.The results show that the LFMP with cornstalk as the carbon source has better performance compared to the sucrose-coated LFMP material(LFMP@C).The discharge capacity of LFMP@C-C is 116 mAh/g for the first cycle at 1 C and the capacity retention rate is 94.0%after 500 cycles,and the discharge capacity of LFMP@C-C is more than 17.17%higher than that of LFMP@C.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22075211,22109118,22275166,21601136,and 51971157)Tianjin Science Fund for Distinguished Young Scholars(No.19JCJQJC61800)+1 种基金Shenzhen Science and Technology Program(Nos.JCYJ20210324123202008,JCYJ20210324115412035,and ZDSYS20210813095534001)Guangdong Foundation for Basic and Applied Basic Research Program(No.2021A1515110880).
文摘As an ideal carbon-free energy carrier,ammonia plays an indispensable role in modern society.The conventional industrial synthesis of NH3 by the Haber-Bosch technique under harsh reaction conditions results in serious energy consumption and environmental pollution.Therefore,it is essential to develop NH3 synthesis tactics under benign conditions.Electrochemical synthesis of NH_(3) has the advantages of mild reaction conditions and environmental friendliness,and has become a hotspot for research in recent years.It has been reported that zinc-nitrogen batteries(ZNBs),such as Zn-N_(2),Zn-NO,Zn-NO_(3)^(-),and Zn-NO_(2)^(-)batteries,can not only reduce nitrogenous species to ammonia but also have concomitant power output.However,the common drawbacks of these battery systems are unsatisfactory power density and ammonia production.In this review,the latest progress of ZNBs including the reaction mechanism of the battery and reactor design principles is systematically summarized.Subsequently,active site engineering of cathode catalysts is discussed,including vacancy defects,chemical doping,and heterostructure engineering.Finally,some insights are provided to improve the performance of ZNBs from a practical perspective of view.
基金Universiti Malaysia Terengganu(UMT)for the funding provided by Golden Goose Research Grant(GGRG)VOT 55190。
文摘Magnesium hydride(MgH_(2))is the most feasible and effective solid-state hydrogen storage material,which has excellent reversibility but initiates decomposing at high temperatures and has slow kinetics performance.Here,zinc titanate(Zn_(2)TiO_(4))synthesised by the solid-state method was used as an additive to lower the initial temperature for dehydrogenation and enhance the re/dehydrogenation behaviour of MgH_(2).With the presence of Zn_(2)TiO_(4),the starting temperature for the dehydrogenation of MgH_(2)was remarkably lowered to around 290℃–305℃.In addition,within 300 s,the MgH_(2)–Zn_(2)TiO_(4)sample absorbed 5.0 wt.%of H_(2)and 2.2–3.6 wt.%H_(2)was liberated from the composite sample in 30 min,which is faster by 22–36 times than as-milled MgH_(2).The activation energy of the MgH_(2)for the dehydrogenation process was also downshifted to 105.5 k J/mol with the addition of Zn_(2)TiO_(4)indicating a decrease of 22%than as-milled MgH_(2).The superior behaviour of MgH_(2)was due to the formation of Mg Zn_(2),MgO and MgTiO_(3),which are responsible for ameliorating the re/dehydrogenation behaviour of MgH_(2).These findings provide a new understanding of the hydrogen storage behaviour of the catalysed-MgH_(2)system.
基金the financial supports from the Key Research and Development Program of Guangxi(No.GUIKE AB22080061)the Guangxi Transportation Industry Key Science and Technology Projects(No.GXJT-2020-02-08)+2 种基金the National Natural Science Foundation of China(No.52268062)the Guangxi Key Project of Nature Science Foundation(No.2020GXNSFDA238024)。
文摘To improve the soil and water stability of expansive soil slopes and reduce the probability of slope failure,novel protection systems based on polymer waterproof coatings(PWC)were used in this study.Herein,three groups of expansive soil slope model tests were designed to investigate the effects of polyester nonwovens and PWC(P-PWC)composite protection system,three-dimensional vegetation network and PWC(T-PWC)composite protection system,and nonprotection on the soil and water behavior in the slopes under precipitation–evaporation cycles.The results showed that the moisture change of P-PWC and T-PWC composite protected slopes was significantly smaller than that of bare slope,which reduced the sensitivity of slope moisture to environmental changes and improved its stability.The soil temperature of the slope protected by the P-PWC and T-PWC systems at a depth of 70 cm increased by 5.6℃ and 2.7℃,respectively.Using PWC composite protection systems exhibited better thermal storage performance,which could increase the utilization of shallow geothermal resources.Moreover,the maximum average crack widths of the bare slopes were 7.89 and 3.17 times those of the P-PWC and TPWC protected slopes,respectively,and the maximum average crack depths were 6.87 and 3 times those of the P-PWC and T-PWC protected slopes,separately.The PPWC protection system weakened the influence of hydro–thermal coupling on the slopes,inhibited the development of cracks on the slopes,and reduced the soil erosion.The maximum soil erosion of slopes protected by P-PWC and T-PWC systems was 332 and 164 times lower than that of bare slope,respectively.The P-PWC and T-PWC protection systems achieved excellent"anti-seepage and moisture retention"and anti-erosion effects,thus improving the soil and water stability of slopes.These findings can provide important guiding reference for controlling rainwater infiltration and soil erosion in expansive soil slope projects.
基金supported by the National Natural Science Foundation of China(Grant No.52062002 and 51961006)the Open Foundation of Guangxi Key Laboratory of Processing for Nonferrous Metals and Featured Materials,Guangxi University,China(2021GXYSOF01).
文摘A series of single-phase double perovskite Pr1-xGdxBaCo_(2)-yFeyO_(5+σ)(x=0,0.5 and 1,0≤y≤1)materials were engineered through A/B site co-doping strategy to improve the mechanical,electrical and electrochemical properties as potential cathode materials for the application of intermediate solid oxide fuel cells(IT-SOFCs).The corresponding thermochemical stability,thermal expansion behavior,electrical conductivity and cathodic polarization resistance of the materials were systematically investigated.It was found that the A-site dual lanthanide doped Pr_(0.5)Gd_(0.5)BaCo_(2)O_(5+σ)(PGBCO)exhibits improved electrical conductivity,reduced thermal expansion,and comparatively low electrochemical polarization resistance versus single lanthanide double perovskite,PrBaCo_(2)O_(5+σ)(PBCO)and GdBaCo_(2)O_(5+σ)(GBCO)materials.Further investigation on the effect of B-site Fe-doping on Pr_(0.5)Gd_(0.5)BaCo_(2)-yFeyO_(5)+σ(PGBCF-y,0≤y≤1)reveals that all the PGBCF-y compositions exhibit excellent chemical stability with Gd-doped ceria(GDC)at operating temperatures not higher than 1100℃.Besides,doping of Fe in B-site can effectively reduce the thermal expansion coefficients(TECs)of the Pr_(0.5)Gd_(0.5)BaCo_(2)O_(5)+σceramics at 30e1000℃.And the electrochemical impedance spectra(EIS)results show that the PGBCF-y|GDC|PGBCF-y symmetric cells have acceptable low area specific polarization resistances.Further examination of the cathodic polarization and characteristic capacitance from the AC impedance spectra by employing the relaxation time distribution(DRT)method demonstrated that charge transfer is the dominating subprocess for the oxygen transport through the materials.
基金supported by National Key Research and Development Program of China(No.2017YFE0198000,2022YFE0119100).National Natural Science Foundation of China(Grant No.U21A2054,52273285,52061009,52262032).Guangxi Science and Technology Project(Grant No.AD21220056).
文摘SiGe is recognised as an excellent thermoelectric material with superior mechanical properties and thermal stability in regions with high temperatures.This study explores a novel strategy for coregulating thermoelectric transport parameters to achieve high thermoelectric properties of p-type SiGe in the mid-temperature region by incorporating nano-TaC into SiGe combined ball milling with spark plasma sintering.By optimizing the amount of TaC in the SiGe matrix,the power factors were significantly increased due to the modulation doping effect based on the work function matching of SiGe with TaC.Simultaneously,the ensemble effect of the nanostructure leads to a significant decrease in thermal conductivity.Thus,a high ZT of 1.06 was accomplished at 873 K,which is 64%higher than that of typical radioisotope thermoelectric generator.Our research offers a novel strategy for expanding and enhancing the thermoelectric properties of SiGe materials in the medium temperature range.
基金supported by the National Natural Science Foundation of China(Grant Nos.51971157 and 22075211)Shenzhen Science and Technology Program(Grant Nos.JCYJ20210324115412035,JCYJ20210324123202008,JCYJ20210324122803009 and ZDSYS20210813095534001)Guangdong Foundation for Basic and Applied Basic Research Program(Grant No.2021A1515110880).
文摘Layered double hydroxides have demonstrated great potential for the oxygen evolution reaction,which is a crucial half-reaction of overall water splitting.However,it remains challenging to apply layered double hydroxides in other electrochemical reactions with high efficiency and stability.Herein,we report two-dimensional multifunctional layered double hydroxides derived from metalorganic framework sheet precursors supported by nanoporous gold with high porosity,which exhibit appealing performances toward oxygen/hydrogen evolution reactions,hydrazine oxidation reaction,and overall hydrazine splitting.The as-prepared catalyst only requires an overpotential of 233 mV to reach 10 mA·cm^(-2) toward oxygen evolution reaction.The overall hydrazine splitting cell only needs a cell voltage of 0.984 V to deliver 10 mA·cm^(-2),which is far more superior than that of the overall water splitting system(1.849 V).The appealing performances of the catalyst can be contributed to the synergistic effect between the metal components of the layered double hydroxides and the supporting effect of the nanoporous gold substrate,which could endow the sample with high surface area and excellent conductivity,resulting in superior activity and stability.
基金supported by the National Natural Science Foundation of China(Nos.22075211 and 51971157)the Guangzhou Basic&Applied Basic Research Project(No.202201011853)+2 种基金the Shenzhen Science and Technology Program(Nos.JCYJ20210324115412035,JCYJ20210324123202008,JCYJ20210324122803009,and ZDSYS20210813095534001)the Guangdong Basic and Applied Basic Research Foundation(No.2021A1515110880)the Tianjin Science Fund for Distinguished Young Scholars(No.19JCJQJC61800).
文摘Electrocatalytic nitrate reduction reaction(NO_(3)RR)offers a unique rationale for green NH_(3) synthesis,yet the lack of high-efficiency NO_(3)RR catalysts remains a great challenge.In this work,we show that Au nanoclusters anchored on TiO_(2) nanosheets can efficiently catalyze the conversion of NO_(3)RR-to-NH_(3) under ambient conditions,achieving a maximal Faradic efficiency of 91%,a peak yield rate of 1923μg·h^(-1)·mgcat.-1,and high durability over 10 consecutive cycles,all of which are comparable to the recently reported metrics(including transition metal and noble metal-based catalysts)and exceed those of pristine TiO_(2).Moreover,a galvanic Zn-nitrate battery using the catalyst as the cathode was proposed,which shows a power density of 3.62 mW·cm^(-2) and a yield rate of 452μg·h^(-1)·mgcat.-1.Theoretical simulations further indicate that the atomically dispersed Au clusters can promote the adsorption and activation of NO_(3)-species,and reduce the NO_(3)RR-to-NH_(3) barrier,thus leading to an accelerated cathodic reaction.This work highlights the importance of metal clusters for the NH_(3) electrosynthesis and nitrate removal.
基金supported by Specific Research Project of Guangxi for Research Bases and Talents(Grant No.GuiKe AD19245145)Natural Science Foundation of Guangxi Province(Grant No.2018GXNSFBA281106).
文摘To improve the strength-toughness of 13Cr4NiMo martensitic stainless steel(13-4MSS),a thermal cyclic heat treatment(TCHT)combined with the advantage of tempering was proposed.The microstructures were characterized by scanning electron microscopy,X-ray diffraction and electron backscattered diffraction,and the mechanical behaviors in terms of tensile properties and impact toughness were analyzed in correlation with microstructural evolution.It was found that grains and the martensitic matrix were refined by TCHT through the cyclic quenching transformation and austenite recrystallization,which was conducive to more nucleation quantity of reversed austenite during tempering.Two-sphericalcap nucleation model was used to explain the effect of refined grains of TCHT on the nucleation of reversed austenite.Grain refinement by TCHT improved the brittle fracture stress to reduce the ductile-brittle transition temperature and thus improved the cryogenic impact toughness of 13-4MSS.Reversed austenite distributed at the martensitic lath boundary enhances the crack arrest performance and increases the britle fracture stress.It is concluded that reasonable TCHT plus tempering process significantly improves the strength-toughness of 13-4MSS,reflecting the comprehensive effect of grain refinement and reversed austenite.
基金This work was supported by the Natural Science Foundation of Guangxi(Grant No.2018GXNSFBA138025)the National Natural Science Foundation of China(Grant No.32171720).
文摘The combination of high-voltage windows and bending stability remains a challenge for supercapacitors.Here,we present an“advantage-complementary strategy”using sodium lignosulfonate as a pseudocapacitive molecule to regulate the spatial stacking pattern of graphene oxide and the interfacial architectures of graphene oxide and polyaniline.Flexible and sustainable sodium lignosulfonate-based electrodes are successfully developed,showing perfect bending stability and high electronic conductivity and specific capacitance(521 F·g^(−1)at 0.5 A·g^(−1)).Due to the resulting rational interfacial structure and stable ion-electron transport,the asymmetric supercapacitors provide a wide voltage window reaching 1.7 V,outstanding bending stability and high energy-power density of 83.87 Wh·kg^(−1)at 3.4 kW·kg^(−1).These properties are superior to other reported cases of asymmetric energy enrichment.The synergistic strategy of sodium lignosulfonate on graphene oxide and polyaniline is undoubtedly beneficial to advance the process for the construction of green flexible supercapacitors with remarkably wide voltage windows and excellent bending stability.
基金The authors gratefully acknowledge the financial supports provided by the National Natural Science Foundation of China(No.21902119)Guangxi Provincial Natural Science Foundation(No.GUIKEAD22035044)Advanced Innovation Teams and Xinghu Scholars Program of Guangxi Medical University,and start-up funding for high-level talents from Guangxi Medical University Cancer Hospital。
文摘Facilitated by reactive oxygen species(ROS)-involved therapies,tumor cells undergo immunogenic cell death(ICD)to stimulate long-term immunity response.However,it is hard to trigger abundant and large-scale ICD for satisfactory cancer immunotherapy.Herein,a multifunctional sonosensitizer that consists of Au single atoms and clusters anchored on TiO_(2)nanosheets(named Au_(S/C)-TiO_(2))is reported for augmented sonodynamic therapy(SDT)and glucose depletion,which ultimately induce robust ICD due to the improved ROS generation and strong endoplasmic reticulum(ER)stress.The synergy effect between Au cluster/single atom with TiO_(2)nanosheets intensifies apoptosis and ICD pathways to inhibit 80%of tumor cells through in vivo analyses.Furthermore,immune cells in vivo analyses verify the effectiveness of Au_(S/C)-TiO_(2)sonosensitizer towards the induction of antitumor immunity.This study thus reveals that simultaneous presence of ROS generation and strong ER stress can efficiently evoke a strong ICD-mediated immune response.
基金supported by the Guangxi NSF(No.2020GXNSFDA238004)the Bagui Scholar project of Guangxi provincethe Scientific and Technological Bases and Talents of Guangxi(No.Guike AD21238027).
文摘Sb-based organic–inorganic hybrid metal halides(OIHMHs)with[SbCl5]2−units have been widely reported due to high photoluminescence quantum yield(PLQY)and occasional multiple self-trapped exciton(STE)emission bands mainly out of singlet and triplet states,and their multi-band emission is important in white light-emitting diode(WLED).However,not all these OIHMH compounds can produce both emissions out of singlet STE and triplet STE at room temperature simultaneously.It is crucial to consider how the singlet STE generates and retains to emit light at room temperature for this material’s design and application.Herein,a strategy is proposed that can significantly lift Sb halide PLQY by synthesizing two Sb-based OIHMHs using organic amine cations of different-sized and-quantity,which modulate the distance of neighboring emission centers.Therein,the occurrence of singlet STE emission is found to be closely related to the distance of[SbCl_(5)]^(2)−units and local unit distortion in the lattice.The larger distance can produce smaller local distortions,favoring the formation of the singlet STE emission band at higher energy.This is the first work to reveal the relationship between the local structure and the origin of the singlet STE emission band,providing new insights into the modulation of the Sb-based OIHMH’s emission.
