Vanadium is a strategic metal in many countries,and it is mainly extracted from vanadium slag produced in titanomagnetite metallurgy.The traditional sodium roasting process for vanadium extraction poses environmental ...Vanadium is a strategic metal in many countries,and it is mainly extracted from vanadium slag produced in titanomagnetite metallurgy.The traditional sodium roasting process for vanadium extraction poses environmental threats,and a green calcification pro-cess has been proposed.However,the vanadium extraction rate in the calcification process is much lower than in the sodium roasting pro-cess,which is related to vanadium solid solubility in Fe_(2)TiO_(5).Previous studies about vanadium behavior in Fe_(2)TiO_(5) were conducted in air,with a vanadium oxidation state of V5+.Vanadium with lower oxidation states has been detected in the tailings in the calcification process.The present paper studied the effects of vanadium oxidation states on the solid solubility in Fe_(2)TiO_(5) through solid-state reaction,X-ray diffraction characterization,transmission electron microscopy characterization,X-ray photoelectron spectroscopy analysis,and solid solu-tion modeling.The relative interaction values between vanadium oxides and Fe_(2)TiO_(5) are obtained as|L_(V_(2)O_(3))|>|L_(V_(2)O_(4))|>|L_(V_(2)O_(5)),indicating that vanadium with lower valence is preferable to be solid dissolved in Fe_(2)TiO_(5).The results imply that insufficiently oxidized vanadium increases the vanadium content in the Fe_(2)TiO_(5) phase during vanadium slag’s calcification roasting.Besides,experimental conditions op-timization shows that higher experimental temperature,vanadium introduction as V2O3,and a high-purity argon atmosphere would lead to higher vanadium solubility in Fe_(2)TiO_(5),and high temperature is beneficial for the release of vanadium from vanadium-containing Fe_(2)TiO_(5) when dissociated in air.展开更多
AV4+-V2O5 cathode with mixed vanadium valences was prepared via a novel synthetic method using VOOH as the precursor,and its zinc-ion storage performance was evaluated.The products are hollow spheres consisting of nan...AV4+-V2O5 cathode with mixed vanadium valences was prepared via a novel synthetic method using VOOH as the precursor,and its zinc-ion storage performance was evaluated.The products are hollow spheres consisting of nanoflakes.The V4+-V2O5 cathode exhibits a prominent cycling performance,with a specific capacity of 140 mAhg-1 after 1000 cycles at 10 A g.1,and an excellent rate capability.The good electrochemical performance is attributed to the presence of V4+,which leads to higher electrochemical activity,lower polarization,faster ion diffusion,and higher electrical conductivity than V2O5 without V4+.This engineering strategy of valence state manipulation may pave the way for designing high-performance cathodes for elucidating advanced battery chemistry.展开更多
The valences of Cu in Y_(1-x)Ca_(x)Ba_(2)Cu_(3)O_(6+y) have been investigated by using complex chemical bond theory.The results for the valences of Cu(1)and Cu(2)in the calculation suggest that the holes introduced by...The valences of Cu in Y_(1-x)Ca_(x)Ba_(2)Cu_(3)O_(6+y) have been investigated by using complex chemical bond theory.The results for the valences of Cu(1)and Cu(2)in the calculation suggest that the holes introduced by calcium substitution only reside in CuO_(2) planes,and there is a competition mechanism for the hole density in CuO_(2) planes between Ca doping and oxygen depletion.These conclusions are satisfactorily in agreement with experiments.展开更多
Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(...Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(CO_(2)).With a maximal EDA conversion of 82%and EU selectivity of 99%at 160℃ for 2 h,Mn_(2)O_(3) catalysts had the best catalytic activity among them,which was superior to the reported catalysts.In the following order:Mn_(2)O_(3)>MnO_(2)>Mn_(3)O_(4),the catalytic activity for the synthesis of EU from CO_(2) and EDA decreased.Further characterization showed the Mn_(2)O_(3) catalyst possessed a greater Mn^(3+)/Mn4+ratio and more surface oxygen vacancies than the MnO_(2) and Mn_(3)O_(4),which improved its capacity to adsorb and activate CO_(2) and EDA.After four recycling runs,the EDA conversion slightly declined from 82%to 56%on Mn_(2)O_(3) catalyst,while no obvious change in EU selectivity was observed.The loss of surface Ov contents and Mn^(3+)proportion were concluded as main reasons for the decrease in catalytic activity over Mn_(2)O_(3) catalyst.This work demonstrated a metal oxide catalyst that was efficient in producing EU from CO_(2) and EDA.展开更多
Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as high...Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as highly efficient photocatalysts for hydrogen evolution.However,their applications in photocatalytic hydrogen evolution(PHE)are infrequently documented and the corresponding photocatalytic mechanism has not yet been explored.Herein,we excavated a novel NOS photocatalyst of(Me_(2)NH_(2))_(6)In_(10)S_(18)(MIS)with a three-dimensional(3D)structure,and successfully incorporated divalent Co(Ⅱ)and metal Co(0)into its cavities via the convenient cation exchange-assisted approach to regulate the critical steps of photocatalytic reactions.As the introduced Co(0)allows for more efficient light utilization and adroitly surficial hydrogen desorption,and meanwhile acts as the‘electron pump’for rapid charge transfer,Co(0)-modified MIS delivers a surprising PHE activity in the initial stage of photocatalysis.With the prolonging of illumination,metal Co(0)gradually escapes from MIS framework,resulting in the decline of PHE performance.By stark contrast,the incorporated Co(Ⅱ)can establish a strong interaction with MIS framework,and simultaneously capture photogenerated electrons from MIS to produce Co(0),which constructs a stable photocatalytic system as well as provides additional channels for spatially separating photogenerated carriers.Thus,Co(Ⅱ)-modified MIS exhibits a robust and highly stable PHE activity of~4944μmol/g/h during the long-term photocatalytic reactions,surpassing most of the previously reported In–S framework photocatalysts.This work represents a breakthrough in the study of PHE performance and mechanism of NOS-based photocatalysts,and sheds light on the design of vip confined NOS-based photocatalysts towards high-efficiency solar-to-chemical energy conversion.展开更多
Si,as the most promising anode with high theoretical capacity for next-generation lithium-ion batteries(LIBs),is hampered in commercial application by its poor electrical conductivity and significant volume expansion....Si,as the most promising anode with high theoretical capacity for next-generation lithium-ion batteries(LIBs),is hampered in commercial application by its poor electrical conductivity and significant volume expansion.Herein,the core-shell Si@SiO_(x)/C@C-Ar(SSC-A)or Si@SiO_(x)/C@C-H_(2)/Ar(SSC-H)composites are purposefully designed by in situ introduction of inorganic SiO_(x)in pure Ar or H_(2)/Ar atmosphere to realize a Si-based anode for LIBs.By introducing different atmospheres,the valence states of SiO_(x)are regulated.The inorganic transition layer formed by the combination of SiO_(x)with higher average valence and asphalt-derived carbon demonstrates better performance in both stabilizing the core-shell structure and inhibiting the agglomeration of Si particles.Given these advantages,the SSC-A electrode exhibits excellent electrochemical performance(1163 mAh g^(-1)after 400 cycles at 1 A g^(-1)),and the commercial blended graphite-SSC-A electrode reaches a specific capacity of 442 mAh g^(-1)with 74.8%capacity retention under the same conditions.Even the SSC-A electrode without Super P maintains an ultrahigh discharge specific capacity of 803 mAh g^(-1)with 60.6%after cycling.Importantly,the full batteries based on SSC-A without Super P achieve a discharge specific capacity of 126 mAh g^(-1)with 28.2%capacity decay after 200 cycles,demonstrating the superior commercial application potential.展开更多
The recently established theory has built clear connections between hardness and toughness and electron structure involving both valence electron concentration(VEC)and core electron count(CEC)in transition metal nitri...The recently established theory has built clear connections between hardness and toughness and electron structure involving both valence electron concentration(VEC)and core electron count(CEC)in transition metal nitride(TMN)ceramics.However,the underlying deformation mechanisms remain unclear.Herein,we conduct in-depth analysis on microstructure evolution during deformation of the high VEC-CEC solution TiMoN coatings having desired combination of high hardness and toughness.The effects of solid solution,preferred orientation linked with symbiotic compressive stress,grain size and dislocations are systematically discussed.We discover that numerous dislocations have been implanted into the nanocrystals of the TiMoN coating during the high-ionization arc deposition.Using two-beam bright-field imaging,we count the dislocation density and confirm occurrence of dislocation multiplication to form effective plastic deformation,which contributes to significant strain hardening,comparable to solid solution hardening,fine-grain hardening and compressive stress hardening.The improved dislocation activities also play a crucial role in enhancing the toughness by providing extra energy dissipation paths.This work gains new insights into the origins of mechanical properties of ceramic coatings and possibility to tune them via defects.展开更多
Graphene-metal based materials have been utilized in lithium-sulfur(Li–S)batteries owing to their integrated functionalities thus far.However,their synthesis has predominantly relied on wet-chemistry routes,which lim...Graphene-metal based materials have been utilized in lithium-sulfur(Li–S)batteries owing to their integrated functionalities thus far.However,their synthesis has predominantly relied on wet-chemistry routes,which limited their practical activity in Li–S reaction systems.In this study,we introduce a chemical vapor deposition(CVD)-triggered dry-chemistry approach for the preparation of graphene-cobalt(Co)based catalysts.The versatile CVD technique provides a dry and controllable reaction environment,effectively pledging the compact and clean catalytic interfaces between graphene and Co-based components.Additionally,programmed reactions introduce defects such as vacancies and nitrogen heteroatoms into the catalysts.Notably,the graphene layer number and Co valence state can be delicately manipulated by altering the CVD reaction temperature.Specifically,few-layer graphene wrapped Co/Co_(3)O_(4)(FGr-Co/Co_(3)O_(4))prepared at 450 ℃ shows higher catalytic activity than the multi-layer graphene wrapped Co/CoO(MGr-Co/CoO)synthesized at 550 ℃,attributed to its comprehensive control of clean interface,valence distribution range and defects.Leveraging these advantages,the battery with FGr-Co/Co_(3)O_(4)shows favorable working stability with a degradation rate of only 0.08%over 500 cycles at 1.0 C.Furthermore,under an elevated sulfur loading of 6.1 mg cm^(–2),the battery harvests a remarkable areal capacity of 5.9 mA h cm^(–2)along with stable cyclic operation.展开更多
In this work,we proposed a method to enhance the magnetic properties of(Nd,Ce)-Fe-B magnets with Ce/TRE ratios below 25 wt%by introducing a moderate amount of La elements.The segregation behavior of La elements toward...In this work,we proposed a method to enhance the magnetic properties of(Nd,Ce)-Fe-B magnets with Ce/TRE ratios below 25 wt%by introducing a moderate amount of La elements.The segregation behavior of La elements towards grain boundaries(GBs)was utilized to optimize the GB phase structure.Incorporation of La atoms into the main phase induces lattice expansion,leading to an increased formation of Ce^(3+)ions with enhanced magnetic moments.Comparative analysis with the original magnet(La/Ce=0 wt%)demonstrates that the magnet with a La/Ce ratio of 10 wt%exhibits improvements of 0.3%in remanence,12.6%in coercivity,and 0.6%in maximum energy produ ct.These results underscore that the moderate addition of La elements enhances the fluidity of the rare earth-rich phase and optimizes the distribution of lamellar GB,consequently reinforcing the magnetic isolation effect.Furthermore,the promotion of the transformation from Ce^(4+)to Ce^(3+)ons contributes to the comprehensive enhancement of the magnetic properties.This research offers a novel strategy for fabricating high-performance and resource-e fficient sintered magnets based on LaCe alloys.展开更多
Single-atom catalysts(SACs)have attracted considerable interest in the fields of energy and environmental science due to their adjustable catalytic activity.In this study,we investigated the matching of valence electr...Single-atom catalysts(SACs)have attracted considerable interest in the fields of energy and environmental science due to their adjustable catalytic activity.In this study,we investigated the matching of valence electron numbers between single atoms and adsorbed intermediates(O,N,C,and H)in MXene-anchored SACs(M-Ti_(2)C/M-Ti_(2)CO_(2)).The density functional theory results demonstrated that the sum of the valence electron number(VM)of the interface-doped metal and the valence electron number(VA)of the adsorbed intermediates in M-Ti_(2)C followed the 10-valence electron matching law.Furthermore,based on the 10-valence electron matching law,we deduced that the sum of the valence electron number(k)and VMfor the molecular adsorption intermediate interactions in M-Ti_(2)CO_(2)adhered to the 11-valence electron matching law.Electrostatic repulsion between the interface electrons in M-Ti_(2)CO_(2)and H_(2)O weakened the adsorption of intermediates,Furthermore,we applied the 11-valence electron matching law to guide the design of catalysts for nitrogen reduction reaction,specifically for N_(2)→NNH conversion,in the MTi_(2)CO_(2)structure.The sure independence screening and sparsifying operator algorithm was used to fit a simple three-dimensional descriptor of the adsorbate(R_(2)up to 0.970)for catalyst design.Our study introduced a valence electron matching principle between doped metals(single atoms)and adsorbed intermediates(atomic and molecular)for MXene-based catalysts,providing new insights into the design of high-performance SACs.展开更多
The capacity to predict X-ray transition and K-edge energies in dense finite-temperatur plasmas with high precision is of primary importance for atomic physics of matter under extreme conditions.The dual characteristi...The capacity to predict X-ray transition and K-edge energies in dense finite-temperatur plasmas with high precision is of primary importance for atomic physics of matter under extreme conditions.The dual characteristics of bound and continuum states in dense matter are modeled by a valence-band-like structure in a generalized ion-sphere approach with states that are either bound,free,or mixed.The self-consistent combination of this model with the Dirac wave equations of multielectron bound states allows one to fully respect the Pauli principle and to take into account the exact nonlocal exchange terms.The generalized method allows very high precision without implication of calibration shifts and scaling parameters and therefore has predictive power.This leads to new insights in the analysis of various data.The simple ionization model representing the K-edge is generalized to excitation–ionization phenomena resulting in an advanced interpretation of ionization depression data in near-solid-density plasmas.The model predicts scaling relations along the isoelectronic sequences and the existence of bound M-states that are in excellent agreement with experimental data,whereas other methods have failed.The application to unexplained data from compound materials also gives good agreement without the need to invoke any additional assumptions in the generalized model,whereas other methods have lacked consistency.展开更多
Cu metal and its oxides have attracted much attention for photocatalytic CO_(2)reduction reaction(CO_(2)RR),but the stability and effects of Cu oxidation states on CO_(2)RR are not fully understood.Cu^(x+)/Cu^(0)-load...Cu metal and its oxides have attracted much attention for photocatalytic CO_(2)reduction reaction(CO_(2)RR),but the stability and effects of Cu oxidation states on CO_(2)RR are not fully understood.Cu^(x+)/Cu^(0)-loaded graphitic carbon nitride(g-C_(3)N_(4))heterojunctions(Cu-CuO_(x)/g-C_(3)N_(4))are fabricated via a stepwise calcination method for efficient photocatalytic CO_(2)RR.Cu_(2)O is the main component of Cu-CuO_(x)and the mixed valence Cu includes Cu^(0),Cu^(+),and Cu^(2+),which play the role of charge trapping sites and redox catalytic centers during the photocatalytic CO_(2)RR process.The main products were CO and CH_(4)for the CO_(2)RR with production rates of 14.45 and 0.66μmol g^(-1)h^(-1)for CO and CH_(4),which were higher than those for g-C_(3)N_(4)and Cu-CuO_(x),respectively.This photocatalytic CO_(2)RR performance is attributed to the ultrafast switching of“Cu^(x+)−Cu^(0)”and e_(CB^(−))/h_(VB^(+))trapping transformation in Cu-CuO_(x)benefited from the built-in IEF between Cu-CuO_(x)and g-C_(3)N_(4),increasing the efficient photogenerated e_(CB^(−)),and enabling the stability of Cu-CuO_(x)/g-C_(3)N_(4).Cu^(x+)adsorbed by H_(2)O works as the electron trapping site to change to Cu^(0)and switch to the hole trapping site;Cu^(0)works as the hole trapping site to change to Cu^(x+)and switch to the electron trapping site,causing the CO_(2)RR of the adsorbed CO_(2).Moreover,the coordinated Cu^(0)and Cu^(+)species facilitate the activation of the adsorbed CO_(2)and^(∗)CO generation,these adsorbed^(∗)CO on Cu^(0)and Cu^(+)detected by in-situ DRIFTS quickly transformed to^(∗)CHO with a lower energy barrier benefited from the mixed Cu^(0)/Cu^(+)active sites during CORR to produce CH_(4).This finding provides a new insight into the influence of mixed valence Cu during photocatalytic CO_(2)RR.展开更多
The mechanical,thermodynamic properties and electrical conductivities of L1_(2)-Al_(3)X(X=Zr,Sc,Er,Yb,Hf)structural phases in aluminum conductors were investigated through a first-principles study.The results demonstr...The mechanical,thermodynamic properties and electrical conductivities of L1_(2)-Al_(3)X(X=Zr,Sc,Er,Yb,Hf)structural phases in aluminum conductors were investigated through a first-principles study.The results demonstrate that all structural phases have good alloy-forming ability and structural stability,where Al_(3)Zr is the most superior.Al_(3)Zr,Al_(3)Hf and Al_(3)Sc have enhanced shear and deformation resistance in comparison to other phases.Within the temperature range of 200−600 K,Al_(3)Er and Al_(3)Yb possess the greatest thermodynamic stability,followed by Al_(3)Hf,Al_(3)Zr and Al_(3)Sc.Al_(3)Er and Al_(3)Yb have higher thermodynamic stability than Al_(3)Hf,Al_(3)Zr and Al_(3)Sc.All structural phases exhibit substantial metallic properties,indicating their good electrical conductivity.The electrical conductivities of Al_(3)Hf and Al_(3)Zr are higher than those of Al_(3)Er,Al_(3)Yb and Al_(3)Sc.The covalent bond properties in Al_(3)Sc,Al_(3)Er and Al_(3)Yb enhance the hardness,brittleness and thermodynamic stability of the structural phase.The thermodynamic stability of Al_(3)Sc is significantly reduced by ionic bonds.展开更多
Herein,we established a Zn_(3)(OH)_(2)(V_(2)O_(7))(H_(2)O)_(2)/V-Zn(O,S)Z-scheme heterojunction labeled ZnVO/V-Zn(O,S)with a heterovalent V^(4+)/V^(5+)states and oxygen vacancies in both phases via a one-step in-situ ...Herein,we established a Zn_(3)(OH)_(2)(V_(2)O_(7))(H_(2)O)_(2)/V-Zn(O,S)Z-scheme heterojunction labeled ZnVO/V-Zn(O,S)with a heterovalent V^(4+)/V^(5+)states and oxygen vacancies in both phases via a one-step in-situ hydrolysis method.The NaBH_(4) regulated the ZnVO/V-Zn(O,S)-3 with rich Vo and suitable n(V^(4+))/n(V^(5+))ratio achieved an excellent photocatalytic nitrogen fixation activity of 301.7μmol/(g×h)and apparent quantum efficiency of 1.148%at 420 nm without any sacrificial agent,which is 11 times than that of V-Zn(O,S).The Vo acts as the active site to trap and activate N_(2) molecules and to trap and activate H_(2)O to produce the H for N_(2) molecules photocatalytic reduction.The rich Vo defects can also reduce the competitive adsorption of H_(2)O and N_(2) molecules on the surface active site of the catalyst.The heterovalent vanadium states act as the photogenerated electrons,quickly hopping between V^(4+)and V^(5+)to transfer for the photocatalytic N_(2) reduction reaction.Additionally,the Z-scheme heterojunction effectively minimizes photogenerated carrier recombination.These synergistic effects collectively boost the photocatalytic nitrogen fixation activity.This study provides a practical method for designing Z-scheme heterojunctions for efficient photocatalytic N_(2) fixation under mild conditions.展开更多
Ammonia(NH3)serves as a critical component in the fertilizer industry and fume gas denitrification.However,the conventional NH3production process,namely the Haber-Bosch process,leads to considerable energy consumption...Ammonia(NH3)serves as a critical component in the fertilizer industry and fume gas denitrification.However,the conventional NH3production process,namely the Haber-Bosch process,leads to considerable energy consumption and waste gas emissions.To address this,electrocatalytic nitric oxide reduction reaction(NORR)has emerged as a promising strategy to bridge NH3consumption to NH3production,harnessing renewable electricity for a sustainable future.Copper(Cu)stands out as a prominent electrocatalyst for NO reduction,given its exceptional NH3yield and selectivity.However,a crucial aspect that remains insufficiently explored is the effects of morphology and valence states of Cu on the NORR performance.In this investigation,we synthesized CuO nanowires(CuO-NF)and Cu nanocubes(Cu-NF)as cathodes through an in situ growth method.Remarkably,CuO-NF exhibited an impressive NH3yield of 0.50±0.02 mg cm^(-2)h^(-1)at-0.6 V vs.reversible hydrogen electrode(RHE)with faradaic efficiency of29,68%±1,35%,surpassing that of Cu-NF(0.17±0.01 mg cm^(-2)h^(-1),16.18%±1.40%).Throughout the electroreduction process,secondary cubes were generated on the CuO-NF surface,preserving their nanosheet cluster morphology,sustained by an abundant supply of subsurface oxygen(s-O)even after an extended duration of 10 h,until s-O depletion ensued.Conversely,Cu-NF exhibited inadequate s-O content,leading to rapid crystal collapse within the same timeframe.The distinctive current-potential relationship,akin to a volcano-type curve,was attributed to distinct NO hydrogenation mechanisms.Further Tafel analysis revealed the exchange current density(i0)and standard heterogeneous rate constant(k0)for CuO-NF,yielding 3.44×10^(-6)A cm^(-2)and 3.77×10^(-6)cm^(-2)s^(-1)when NORR was driven by overpotentials.These findings revealed the potential of CuO-NF for NO reduction and provided insights into the intricate interplay between crystal morphology,valence states,and electrochemical performance.展开更多
Band convergence is considered to be a strategy with clear benefits for thermoelectric performance,generally favoring the co-optimization of conductivity and Seebeck coefficients,and the conventional means include ele...Band convergence is considered to be a strategy with clear benefits for thermoelectric performance,generally favoring the co-optimization of conductivity and Seebeck coefficients,and the conventional means include elemental filling to regulate the band.However,the influence of the most electronegative fluorine on the CoSb_(3) band remains unclear.We carry out density-functional-theory calculations and show that the valence band maximum gradually shifts downward with the increase of fluorine filling,lastly the valence band maximum converges to the highly degenerated secondary valence bands in fluorine-filled skutterudites.展开更多
Cu^(+)-doped alkali borosilicate glasses with different Na_(2)O contents were prepared by the melting method,and the effects of different R values(R=Na_(2)O/B_(2)O_(3))on the structure,ion presence state and luminesce...Cu^(+)-doped alkali borosilicate glasses with different Na_(2)O contents were prepared by the melting method,and the effects of different R values(R=Na_(2)O/B_(2)O_(3))on the structure,ion presence state and luminescence properties of Cu^(+)-doped alkali borosilicate glasses were investigated.The analysis by FT-IR and Raman spectroscopy shows that,with the increase of R value of the glass,the[BO_(3)]in the structure of Cu^(+)-doped alkali borosilicate glass transforms into[BO_(4)]and the number of non-bridging oxygen in the glass network appears to be slightly increased.The absorption spectra and EPR analysis reveal that the Cu^(+)content in the glass gradually decreases and the Cu^(2+)content gradually increases as the R value of the glass increases.XPS and PL tests further indicate that the transformation of the octahedral coordination structure of Cu^(+)to the octahedral coordination structure of Cu^(2+)and the cubic coordination structure of Cu^(+)occurs in the glass as the R value of the glass increases.This transformation can effectively reduce the concentration quenching phenomenon of Cu^(+)and improve the fluorescence luminescence intensity of the glass samples.Meanwhile,the samples were found to have luminescence tunability as well as good thermal stability.展开更多
Metal-organic frameworks(MOFs)are highly desirable for promising photocatalytic water splitting,but their practical application is greatly limited due to their unstable chemical properties and insufficient visible lig...Metal-organic frameworks(MOFs)are highly desirable for promising photocatalytic water splitting,but their practical application is greatly limited due to their unstable chemical properties and insufficient visible light response as well as low charge-carries utilization,especially in photocatalytic O_(2)production.Herein,we present a post-modification engineering to modulate cerium metalorganic frameworks(Ce-MOFs)for realizing efficient photocatalytic water oxidation to liberate O_(2)by visible light.The one-step partial oxidation strategy is adopted to modify pristine Ce-MOFs,yielding the new Ce-MOFs(MV-Ce-MOFs)with mixed valence of Ce^(3+)/Ce^(4+).Creating the Ce nodes of a mixed valence state can effectively extend the optical absorption to the visible region,expose more catalytically active sites and inhibit the recombination of photoinduced charges.Consequently,the MV-Ce-MOFs exhibit high activity for photocatalytic O_(2)evolution under visible light,manifesting an impressive1.6%apparent quantum efficiency(AQY)under monochromatic irradiation of 405 nm.The regulation engineering of MOF metal node valence heralds a new paradigm for designing MOF-based photocatalysts.展开更多
The molybdenum carbide(Mo_(2)C)has been regarded as one of the most cost-efficient and stable electrocatalyst for the hydrogen evolution reaction(HER)by the virtue of its Pt-like electronic structures.However,the inhe...The molybdenum carbide(Mo_(2)C)has been regarded as one of the most cost-efficient and stable electrocatalyst for the hydrogen evolution reaction(HER)by the virtue of its Pt-like electronic structures.However,the inherent limitation of high density of empty valence band significantly reduces its catalytic reactivity by reason of strong hydrogen desorption resistance.Herein,we propose a multiscale confinement synthesis method to design the nitrogen-rich Mo_(2)C for modulating the band structure via decomposing the pre-coordination bonded polymer in a pressure-tight tube sealing system.Pre-bonded c/N-Mo in the coordination precursor constructs a micro-confinement space,enabling the homogeneous nitrogenization in-situ happened during the formation of Mo_(2)C.Simultaneously,the evolved gases from the precursor decomposition in tube sealing system establish a macro-confinement environment,preventing the lattice N escape and further endowing a continuous nitridation.Combining the multiscale confinement effects,the nitrogen-rich Mo2C displays as high as 25%N-Mo concentration in carbide lattice,leading to a satisfactory band structure.Accordingly,the constructed nitrogen-rich Mo_(2)C reveals an adorable catalytic activity for HER in both alkaline and acid solution.It is anticipated that the multiscale confinement synthesis strategy presents guideline for the rational design of electrocatalysts and beyond.展开更多
基金supported by the National Key Research and Development Program of China(No.2023YFC2908304).
文摘Vanadium is a strategic metal in many countries,and it is mainly extracted from vanadium slag produced in titanomagnetite metallurgy.The traditional sodium roasting process for vanadium extraction poses environmental threats,and a green calcification pro-cess has been proposed.However,the vanadium extraction rate in the calcification process is much lower than in the sodium roasting pro-cess,which is related to vanadium solid solubility in Fe_(2)TiO_(5).Previous studies about vanadium behavior in Fe_(2)TiO_(5) were conducted in air,with a vanadium oxidation state of V5+.Vanadium with lower oxidation states has been detected in the tailings in the calcification process.The present paper studied the effects of vanadium oxidation states on the solid solubility in Fe_(2)TiO_(5) through solid-state reaction,X-ray diffraction characterization,transmission electron microscopy characterization,X-ray photoelectron spectroscopy analysis,and solid solu-tion modeling.The relative interaction values between vanadium oxides and Fe_(2)TiO_(5) are obtained as|L_(V_(2)O_(3))|>|L_(V_(2)O_(4))|>|L_(V_(2)O_(5)),indicating that vanadium with lower valence is preferable to be solid dissolved in Fe_(2)TiO_(5).The results imply that insufficiently oxidized vanadium increases the vanadium content in the Fe_(2)TiO_(5) phase during vanadium slag’s calcification roasting.Besides,experimental conditions op-timization shows that higher experimental temperature,vanadium introduction as V2O3,and a high-purity argon atmosphere would lead to higher vanadium solubility in Fe_(2)TiO_(5),and high temperature is beneficial for the release of vanadium from vanadium-containing Fe_(2)TiO_(5) when dissociated in air.
基金supported by National Natural Science Foundation of China(Nos.51802356,51872334,and 51572299)Innovation-Driven Project of Central South University(No.2018CX004)
文摘AV4+-V2O5 cathode with mixed vanadium valences was prepared via a novel synthetic method using VOOH as the precursor,and its zinc-ion storage performance was evaluated.The products are hollow spheres consisting of nanoflakes.The V4+-V2O5 cathode exhibits a prominent cycling performance,with a specific capacity of 140 mAhg-1 after 1000 cycles at 10 A g.1,and an excellent rate capability.The good electrochemical performance is attributed to the presence of V4+,which leads to higher electrochemical activity,lower polarization,faster ion diffusion,and higher electrical conductivity than V2O5 without V4+.This engineering strategy of valence state manipulation may pave the way for designing high-performance cathodes for elucidating advanced battery chemistry.
文摘The valences of Cu in Y_(1-x)Ca_(x)Ba_(2)Cu_(3)O_(6+y) have been investigated by using complex chemical bond theory.The results for the valences of Cu(1)and Cu(2)in the calculation suggest that the holes introduced by calcium substitution only reside in CuO_(2) planes,and there is a competition mechanism for the hole density in CuO_(2) planes between Ca doping and oxygen depletion.These conclusions are satisfactorily in agreement with experiments.
基金supported by the National Natural Science Foundation of China(No.22278041)the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(No.2022-K78)+1 种基金Jiangsu Province Key Laboratory of Fine Petrochemical Engineering(No.KF2107)the Advanced Catalysis and Green Manufacturing Collab-orative Innovation Center(No.ACGM2022-10-07)。
文摘Herein,a series of manganese oxide catalysts with different valences(Mn_(3)O_(4),Mn_(2)O_(3),and MnO_(2))were designed and synthesized for the synthesis of ethylene urea(EU)from ethylenediamine(EDA)and carbon dioxide(CO_(2)).With a maximal EDA conversion of 82%and EU selectivity of 99%at 160℃ for 2 h,Mn_(2)O_(3) catalysts had the best catalytic activity among them,which was superior to the reported catalysts.In the following order:Mn_(2)O_(3)>MnO_(2)>Mn_(3)O_(4),the catalytic activity for the synthesis of EU from CO_(2) and EDA decreased.Further characterization showed the Mn_(2)O_(3) catalyst possessed a greater Mn^(3+)/Mn4+ratio and more surface oxygen vacancies than the MnO_(2) and Mn_(3)O_(4),which improved its capacity to adsorb and activate CO_(2) and EDA.After four recycling runs,the EDA conversion slightly declined from 82%to 56%on Mn_(2)O_(3) catalyst,while no obvious change in EU selectivity was observed.The loss of surface Ov contents and Mn^(3+)proportion were concluded as main reasons for the decrease in catalytic activity over Mn_(2)O_(3) catalyst.This work demonstrated a metal oxide catalyst that was efficient in producing EU from CO_(2) and EDA.
基金financial supports provided by the Natural Science Foundation of Fujian Province(No.2024J01195)the National Nature Science Foundation of China(No.21905279)+1 种基金Sanming University(Nos.22YG11 and PYT2201)the Education Scientific Research Project of Youth Teachers in the Education Department of Fujian Province(No.JAT220351).
文摘Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as highly efficient photocatalysts for hydrogen evolution.However,their applications in photocatalytic hydrogen evolution(PHE)are infrequently documented and the corresponding photocatalytic mechanism has not yet been explored.Herein,we excavated a novel NOS photocatalyst of(Me_(2)NH_(2))_(6)In_(10)S_(18)(MIS)with a three-dimensional(3D)structure,and successfully incorporated divalent Co(Ⅱ)and metal Co(0)into its cavities via the convenient cation exchange-assisted approach to regulate the critical steps of photocatalytic reactions.As the introduced Co(0)allows for more efficient light utilization and adroitly surficial hydrogen desorption,and meanwhile acts as the‘electron pump’for rapid charge transfer,Co(0)-modified MIS delivers a surprising PHE activity in the initial stage of photocatalysis.With the prolonging of illumination,metal Co(0)gradually escapes from MIS framework,resulting in the decline of PHE performance.By stark contrast,the incorporated Co(Ⅱ)can establish a strong interaction with MIS framework,and simultaneously capture photogenerated electrons from MIS to produce Co(0),which constructs a stable photocatalytic system as well as provides additional channels for spatially separating photogenerated carriers.Thus,Co(Ⅱ)-modified MIS exhibits a robust and highly stable PHE activity of~4944μmol/g/h during the long-term photocatalytic reactions,surpassing most of the previously reported In–S framework photocatalysts.This work represents a breakthrough in the study of PHE performance and mechanism of NOS-based photocatalysts,and sheds light on the design of vip confined NOS-based photocatalysts towards high-efficiency solar-to-chemical energy conversion.
基金financially supported by the National Natural Science Foundation of China(Nos.U22A20145,52072151,52171211,and 52271218)Jinan Independent Innovative Team(No.2020GXRC015)+3 种基金the Major Program of Shandong Province Natural Science Foundation(No.ZR2023ZD43)Natural Science Foumdation of Jiangsu Province(No.BK20241973)High-level Training Talents of'333'Project in Jiangsu Provincethe Science and Technology Program of University of Jinan(No.XKY2119)
文摘Si,as the most promising anode with high theoretical capacity for next-generation lithium-ion batteries(LIBs),is hampered in commercial application by its poor electrical conductivity and significant volume expansion.Herein,the core-shell Si@SiO_(x)/C@C-Ar(SSC-A)or Si@SiO_(x)/C@C-H_(2)/Ar(SSC-H)composites are purposefully designed by in situ introduction of inorganic SiO_(x)in pure Ar or H_(2)/Ar atmosphere to realize a Si-based anode for LIBs.By introducing different atmospheres,the valence states of SiO_(x)are regulated.The inorganic transition layer formed by the combination of SiO_(x)with higher average valence and asphalt-derived carbon demonstrates better performance in both stabilizing the core-shell structure and inhibiting the agglomeration of Si particles.Given these advantages,the SSC-A electrode exhibits excellent electrochemical performance(1163 mAh g^(-1)after 400 cycles at 1 A g^(-1)),and the commercial blended graphite-SSC-A electrode reaches a specific capacity of 442 mAh g^(-1)with 74.8%capacity retention under the same conditions.Even the SSC-A electrode without Super P maintains an ultrahigh discharge specific capacity of 803 mAh g^(-1)with 60.6%after cycling.Importantly,the full batteries based on SSC-A without Super P achieve a discharge specific capacity of 126 mAh g^(-1)with 28.2%capacity decay after 200 cycles,demonstrating the superior commercial application potential.
基金supported by the Distinguished Young Scholars of China(No.52025014)Natural Science Foundation of Zhejiang Province(No.LQ23E010002)Innovation 2025 Major Project of Ningbo(Nos.2022Z011 and 2023Z022).
文摘The recently established theory has built clear connections between hardness and toughness and electron structure involving both valence electron concentration(VEC)and core electron count(CEC)in transition metal nitride(TMN)ceramics.However,the underlying deformation mechanisms remain unclear.Herein,we conduct in-depth analysis on microstructure evolution during deformation of the high VEC-CEC solution TiMoN coatings having desired combination of high hardness and toughness.The effects of solid solution,preferred orientation linked with symbiotic compressive stress,grain size and dislocations are systematically discussed.We discover that numerous dislocations have been implanted into the nanocrystals of the TiMoN coating during the high-ionization arc deposition.Using two-beam bright-field imaging,we count the dislocation density and confirm occurrence of dislocation multiplication to form effective plastic deformation,which contributes to significant strain hardening,comparable to solid solution hardening,fine-grain hardening and compressive stress hardening.The improved dislocation activities also play a crucial role in enhancing the toughness by providing extra energy dissipation paths.This work gains new insights into the origins of mechanical properties of ceramic coatings and possibility to tune them via defects.
基金support of the National Natural Science Foundation of China(Grant No.52172239,52202038,and 52402247)the Innovative Funds Plan of Henan University of Technology(Grant No.2020ZKCJ07)the Natural Science Foundation of Shandong Province(Grant No.ZR2022QE081)。
文摘Graphene-metal based materials have been utilized in lithium-sulfur(Li–S)batteries owing to their integrated functionalities thus far.However,their synthesis has predominantly relied on wet-chemistry routes,which limited their practical activity in Li–S reaction systems.In this study,we introduce a chemical vapor deposition(CVD)-triggered dry-chemistry approach for the preparation of graphene-cobalt(Co)based catalysts.The versatile CVD technique provides a dry and controllable reaction environment,effectively pledging the compact and clean catalytic interfaces between graphene and Co-based components.Additionally,programmed reactions introduce defects such as vacancies and nitrogen heteroatoms into the catalysts.Notably,the graphene layer number and Co valence state can be delicately manipulated by altering the CVD reaction temperature.Specifically,few-layer graphene wrapped Co/Co_(3)O_(4)(FGr-Co/Co_(3)O_(4))prepared at 450 ℃ shows higher catalytic activity than the multi-layer graphene wrapped Co/CoO(MGr-Co/CoO)synthesized at 550 ℃,attributed to its comprehensive control of clean interface,valence distribution range and defects.Leveraging these advantages,the battery with FGr-Co/Co_(3)O_(4)shows favorable working stability with a degradation rate of only 0.08%over 500 cycles at 1.0 C.Furthermore,under an elevated sulfur loading of 6.1 mg cm^(–2),the battery harvests a remarkable areal capacity of 5.9 mA h cm^(–2)along with stable cyclic operation.
基金Project supported by the National Natural Science Foundation of China(52071004,52301228,51971005,52171168)the Program of Top Disciplines Construction in Beijing(PXM2019_014204_500031)the International Research Cooperation Seed Fund of Beijing University of Technology(2021B23)。
文摘In this work,we proposed a method to enhance the magnetic properties of(Nd,Ce)-Fe-B magnets with Ce/TRE ratios below 25 wt%by introducing a moderate amount of La elements.The segregation behavior of La elements towards grain boundaries(GBs)was utilized to optimize the GB phase structure.Incorporation of La atoms into the main phase induces lattice expansion,leading to an increased formation of Ce^(3+)ions with enhanced magnetic moments.Comparative analysis with the original magnet(La/Ce=0 wt%)demonstrates that the magnet with a La/Ce ratio of 10 wt%exhibits improvements of 0.3%in remanence,12.6%in coercivity,and 0.6%in maximum energy produ ct.These results underscore that the moderate addition of La elements enhances the fluidity of the rare earth-rich phase and optimizes the distribution of lamellar GB,consequently reinforcing the magnetic isolation effect.Furthermore,the promotion of the transformation from Ce^(4+)to Ce^(3+)ons contributes to the comprehensive enhancement of the magnetic properties.This research offers a novel strategy for fabricating high-performance and resource-e fficient sintered magnets based on LaCe alloys.
基金funded by the National Natural Science Foundation of China(61701288,51706128)the Natural Science Basic Research Program of Shaanxi Province(2021JM-485)+2 种基金the Key Scientific Research Project of Shaanxi Provincial Education Department(20JS019)the High-level Achievement Cultivation Project of Collaborative Innovation Center for Comprehensive Development of Qinba Biological Resources(QBXT-17-8)the Postgraduate Innovation Project of Shaanxi University of Technology(SLGYCX2410).
文摘Single-atom catalysts(SACs)have attracted considerable interest in the fields of energy and environmental science due to their adjustable catalytic activity.In this study,we investigated the matching of valence electron numbers between single atoms and adsorbed intermediates(O,N,C,and H)in MXene-anchored SACs(M-Ti_(2)C/M-Ti_(2)CO_(2)).The density functional theory results demonstrated that the sum of the valence electron number(VM)of the interface-doped metal and the valence electron number(VA)of the adsorbed intermediates in M-Ti_(2)C followed the 10-valence electron matching law.Furthermore,based on the 10-valence electron matching law,we deduced that the sum of the valence electron number(k)and VMfor the molecular adsorption intermediate interactions in M-Ti_(2)CO_(2)adhered to the 11-valence electron matching law.Electrostatic repulsion between the interface electrons in M-Ti_(2)CO_(2)and H_(2)O weakened the adsorption of intermediates,Furthermore,we applied the 11-valence electron matching law to guide the design of catalysts for nitrogen reduction reaction,specifically for N_(2)→NNH conversion,in the MTi_(2)CO_(2)structure.The sure independence screening and sparsifying operator algorithm was used to fit a simple three-dimensional descriptor of the adsorbate(R_(2)up to 0.970)for catalyst design.Our study introduced a valence electron matching principle between doped metals(single atoms)and adsorbed intermediates(atomic and molecular)for MXene-based catalysts,providing new insights into the design of high-performance SACs.
基金supported by the NSFC under Grant Nos.11374315 and 12074395the Invited Scientist Program of CNRS at Ecole Polytechnique,Palaiseau,France。
文摘The capacity to predict X-ray transition and K-edge energies in dense finite-temperatur plasmas with high precision is of primary importance for atomic physics of matter under extreme conditions.The dual characteristics of bound and continuum states in dense matter are modeled by a valence-band-like structure in a generalized ion-sphere approach with states that are either bound,free,or mixed.The self-consistent combination of this model with the Dirac wave equations of multielectron bound states allows one to fully respect the Pauli principle and to take into account the exact nonlocal exchange terms.The generalized method allows very high precision without implication of calibration shifts and scaling parameters and therefore has predictive power.This leads to new insights in the analysis of various data.The simple ionization model representing the K-edge is generalized to excitation–ionization phenomena resulting in an advanced interpretation of ionization depression data in near-solid-density plasmas.The model predicts scaling relations along the isoelectronic sequences and the existence of bound M-states that are in excellent agreement with experimental data,whereas other methods have failed.The application to unexplained data from compound materials also gives good agreement without the need to invoke any additional assumptions in the generalized model,whereas other methods have lacked consistency.
基金support of the National Natu-ral Science Foundation of China(No.62004143,22476058,and 22076052)the Key R&D Program of Hubei Province(No.2022BAA084).
文摘Cu metal and its oxides have attracted much attention for photocatalytic CO_(2)reduction reaction(CO_(2)RR),but the stability and effects of Cu oxidation states on CO_(2)RR are not fully understood.Cu^(x+)/Cu^(0)-loaded graphitic carbon nitride(g-C_(3)N_(4))heterojunctions(Cu-CuO_(x)/g-C_(3)N_(4))are fabricated via a stepwise calcination method for efficient photocatalytic CO_(2)RR.Cu_(2)O is the main component of Cu-CuO_(x)and the mixed valence Cu includes Cu^(0),Cu^(+),and Cu^(2+),which play the role of charge trapping sites and redox catalytic centers during the photocatalytic CO_(2)RR process.The main products were CO and CH_(4)for the CO_(2)RR with production rates of 14.45 and 0.66μmol g^(-1)h^(-1)for CO and CH_(4),which were higher than those for g-C_(3)N_(4)and Cu-CuO_(x),respectively.This photocatalytic CO_(2)RR performance is attributed to the ultrafast switching of“Cu^(x+)−Cu^(0)”and e_(CB^(−))/h_(VB^(+))trapping transformation in Cu-CuO_(x)benefited from the built-in IEF between Cu-CuO_(x)and g-C_(3)N_(4),increasing the efficient photogenerated e_(CB^(−)),and enabling the stability of Cu-CuO_(x)/g-C_(3)N_(4).Cu^(x+)adsorbed by H_(2)O works as the electron trapping site to change to Cu^(0)and switch to the hole trapping site;Cu^(0)works as the hole trapping site to change to Cu^(x+)and switch to the electron trapping site,causing the CO_(2)RR of the adsorbed CO_(2).Moreover,the coordinated Cu^(0)and Cu^(+)species facilitate the activation of the adsorbed CO_(2)and^(∗)CO generation,these adsorbed^(∗)CO on Cu^(0)and Cu^(+)detected by in-situ DRIFTS quickly transformed to^(∗)CHO with a lower energy barrier benefited from the mixed Cu^(0)/Cu^(+)active sites during CORR to produce CH_(4).This finding provides a new insight into the influence of mixed valence Cu during photocatalytic CO_(2)RR.
基金National Natural Science Foundation of China (No. 52274403)。
文摘The mechanical,thermodynamic properties and electrical conductivities of L1_(2)-Al_(3)X(X=Zr,Sc,Er,Yb,Hf)structural phases in aluminum conductors were investigated through a first-principles study.The results demonstrate that all structural phases have good alloy-forming ability and structural stability,where Al_(3)Zr is the most superior.Al_(3)Zr,Al_(3)Hf and Al_(3)Sc have enhanced shear and deformation resistance in comparison to other phases.Within the temperature range of 200−600 K,Al_(3)Er and Al_(3)Yb possess the greatest thermodynamic stability,followed by Al_(3)Hf,Al_(3)Zr and Al_(3)Sc.Al_(3)Er and Al_(3)Yb have higher thermodynamic stability than Al_(3)Hf,Al_(3)Zr and Al_(3)Sc.All structural phases exhibit substantial metallic properties,indicating their good electrical conductivity.The electrical conductivities of Al_(3)Hf and Al_(3)Zr are higher than those of Al_(3)Er,Al_(3)Yb and Al_(3)Sc.The covalent bond properties in Al_(3)Sc,Al_(3)Er and Al_(3)Yb enhance the hardness,brittleness and thermodynamic stability of the structural phase.The thermodynamic stability of Al_(3)Sc is significantly reduced by ionic bonds.
文摘Herein,we established a Zn_(3)(OH)_(2)(V_(2)O_(7))(H_(2)O)_(2)/V-Zn(O,S)Z-scheme heterojunction labeled ZnVO/V-Zn(O,S)with a heterovalent V^(4+)/V^(5+)states and oxygen vacancies in both phases via a one-step in-situ hydrolysis method.The NaBH_(4) regulated the ZnVO/V-Zn(O,S)-3 with rich Vo and suitable n(V^(4+))/n(V^(5+))ratio achieved an excellent photocatalytic nitrogen fixation activity of 301.7μmol/(g×h)and apparent quantum efficiency of 1.148%at 420 nm without any sacrificial agent,which is 11 times than that of V-Zn(O,S).The Vo acts as the active site to trap and activate N_(2) molecules and to trap and activate H_(2)O to produce the H for N_(2) molecules photocatalytic reduction.The rich Vo defects can also reduce the competitive adsorption of H_(2)O and N_(2) molecules on the surface active site of the catalyst.The heterovalent vanadium states act as the photogenerated electrons,quickly hopping between V^(4+)and V^(5+)to transfer for the photocatalytic N_(2) reduction reaction.Additionally,the Z-scheme heterojunction effectively minimizes photogenerated carrier recombination.These synergistic effects collectively boost the photocatalytic nitrogen fixation activity.This study provides a practical method for designing Z-scheme heterojunctions for efficient photocatalytic N_(2) fixation under mild conditions.
基金supported by the Fundamental Research Funds for the Central Universities(FRF-EYIT-23-07)。
文摘Ammonia(NH3)serves as a critical component in the fertilizer industry and fume gas denitrification.However,the conventional NH3production process,namely the Haber-Bosch process,leads to considerable energy consumption and waste gas emissions.To address this,electrocatalytic nitric oxide reduction reaction(NORR)has emerged as a promising strategy to bridge NH3consumption to NH3production,harnessing renewable electricity for a sustainable future.Copper(Cu)stands out as a prominent electrocatalyst for NO reduction,given its exceptional NH3yield and selectivity.However,a crucial aspect that remains insufficiently explored is the effects of morphology and valence states of Cu on the NORR performance.In this investigation,we synthesized CuO nanowires(CuO-NF)and Cu nanocubes(Cu-NF)as cathodes through an in situ growth method.Remarkably,CuO-NF exhibited an impressive NH3yield of 0.50±0.02 mg cm^(-2)h^(-1)at-0.6 V vs.reversible hydrogen electrode(RHE)with faradaic efficiency of29,68%±1,35%,surpassing that of Cu-NF(0.17±0.01 mg cm^(-2)h^(-1),16.18%±1.40%).Throughout the electroreduction process,secondary cubes were generated on the CuO-NF surface,preserving their nanosheet cluster morphology,sustained by an abundant supply of subsurface oxygen(s-O)even after an extended duration of 10 h,until s-O depletion ensued.Conversely,Cu-NF exhibited inadequate s-O content,leading to rapid crystal collapse within the same timeframe.The distinctive current-potential relationship,akin to a volcano-type curve,was attributed to distinct NO hydrogenation mechanisms.Further Tafel analysis revealed the exchange current density(i0)and standard heterogeneous rate constant(k0)for CuO-NF,yielding 3.44×10^(-6)A cm^(-2)and 3.77×10^(-6)cm^(-2)s^(-1)when NORR was driven by overpotentials.These findings revealed the potential of CuO-NF for NO reduction and provided insights into the intricate interplay between crystal morphology,valence states,and electrochemical performance.
基金supported by the National Natural Science Foundation of China (Grant Nos.52171220,92163212,and 92163119)the Research Funding of Wuhan Polytechnic University (Grant No.2022RZ059)the National Innovation and Entrepreneurship Training Program for College Students (Grant No.S202310497202)。
文摘Band convergence is considered to be a strategy with clear benefits for thermoelectric performance,generally favoring the co-optimization of conductivity and Seebeck coefficients,and the conventional means include elemental filling to regulate the band.However,the influence of the most electronegative fluorine on the CoSb_(3) band remains unclear.We carry out density-functional-theory calculations and show that the valence band maximum gradually shifts downward with the increase of fluorine filling,lastly the valence band maximum converges to the highly degenerated secondary valence bands in fluorine-filled skutterudites.
基金Funded by the Key R&D Projects in Hubei Province of China(No:2020BAB061)。
文摘Cu^(+)-doped alkali borosilicate glasses with different Na_(2)O contents were prepared by the melting method,and the effects of different R values(R=Na_(2)O/B_(2)O_(3))on the structure,ion presence state and luminescence properties of Cu^(+)-doped alkali borosilicate glasses were investigated.The analysis by FT-IR and Raman spectroscopy shows that,with the increase of R value of the glass,the[BO_(3)]in the structure of Cu^(+)-doped alkali borosilicate glass transforms into[BO_(4)]and the number of non-bridging oxygen in the glass network appears to be slightly increased.The absorption spectra and EPR analysis reveal that the Cu^(+)content in the glass gradually decreases and the Cu^(2+)content gradually increases as the R value of the glass increases.XPS and PL tests further indicate that the transformation of the octahedral coordination structure of Cu^(+)to the octahedral coordination structure of Cu^(2+)and the cubic coordination structure of Cu^(+)occurs in the glass as the R value of the glass increases.This transformation can effectively reduce the concentration quenching phenomenon of Cu^(+)and improve the fluorescence luminescence intensity of the glass samples.Meanwhile,the samples were found to have luminescence tunability as well as good thermal stability.
基金financially supported by the Natural Science Foundation of Fujian Province(No.2022J05269)the Research Project of Ningde Normal University(No.2020Y016)+1 种基金the Education&Research Project for Young and Middle-aged Teachers of Fujian(No.JAT200698)the National Natural Science Foundation of China(No.22302154 and 22372085)。
文摘Metal-organic frameworks(MOFs)are highly desirable for promising photocatalytic water splitting,but their practical application is greatly limited due to their unstable chemical properties and insufficient visible light response as well as low charge-carries utilization,especially in photocatalytic O_(2)production.Herein,we present a post-modification engineering to modulate cerium metalorganic frameworks(Ce-MOFs)for realizing efficient photocatalytic water oxidation to liberate O_(2)by visible light.The one-step partial oxidation strategy is adopted to modify pristine Ce-MOFs,yielding the new Ce-MOFs(MV-Ce-MOFs)with mixed valence of Ce^(3+)/Ce^(4+).Creating the Ce nodes of a mixed valence state can effectively extend the optical absorption to the visible region,expose more catalytically active sites and inhibit the recombination of photoinduced charges.Consequently,the MV-Ce-MOFs exhibit high activity for photocatalytic O_(2)evolution under visible light,manifesting an impressive1.6%apparent quantum efficiency(AQY)under monochromatic irradiation of 405 nm.The regulation engineering of MOF metal node valence heralds a new paradigm for designing MOF-based photocatalysts.
基金supported by the National Natural Science Foundation of China(52372201,52125202,52202247)the Natural Science Foundation of Jiangsu Province(1192261031693)the Fundamental Research Funds for the Central Universities(30919011110,1191030558)。
文摘The molybdenum carbide(Mo_(2)C)has been regarded as one of the most cost-efficient and stable electrocatalyst for the hydrogen evolution reaction(HER)by the virtue of its Pt-like electronic structures.However,the inherent limitation of high density of empty valence band significantly reduces its catalytic reactivity by reason of strong hydrogen desorption resistance.Herein,we propose a multiscale confinement synthesis method to design the nitrogen-rich Mo_(2)C for modulating the band structure via decomposing the pre-coordination bonded polymer in a pressure-tight tube sealing system.Pre-bonded c/N-Mo in the coordination precursor constructs a micro-confinement space,enabling the homogeneous nitrogenization in-situ happened during the formation of Mo_(2)C.Simultaneously,the evolved gases from the precursor decomposition in tube sealing system establish a macro-confinement environment,preventing the lattice N escape and further endowing a continuous nitridation.Combining the multiscale confinement effects,the nitrogen-rich Mo2C displays as high as 25%N-Mo concentration in carbide lattice,leading to a satisfactory band structure.Accordingly,the constructed nitrogen-rich Mo_(2)C reveals an adorable catalytic activity for HER in both alkaline and acid solution.It is anticipated that the multiscale confinement synthesis strategy presents guideline for the rational design of electrocatalysts and beyond.
