Crystallinity-defect matching relationship of g-C_(3)N_(4): Experimental and theoretical perspectives

Good crystallinity can reduce the charge recombination centers caused by defects,whilst structures with strong polycondensation have high charge mobility,leading to more charge transfer to the material surface for reaction.Much effort has been put into the preparation of a highly efficient g-C_(3)N_(4) with defects to improve its application potential under the premise in high crystallinity.Hence,this review paper emphasizes the importance to balance the defect and crystallinity of g-C_(3)N_(4).In addition,detailed discussion on the relationship between defects and activity of g-C_(3)N_(4) was carried out based on its applications in environmental purification(e.g.,VOCs oxidation,NO_(x) oxidation,H_(2)O_(2) evolution,sterilization,pesticide oxidation)and energy conversion(H_(2) evolution,N_(2) fixation and CO_(2) reduction).Lastly,the challenge in developing more efficient defective g-C_(3)N_(4) photocatalytic materials is summarized.

Magnetocaloric properties and Griffiths phase of ferrimagnetic cobaltite CaBaCo_(4)O_(7)

We present a study on the magnetocaloric properties of a CaBaCo_(4)O_(7) polycrystalline cobaltite along with research on the nature of magnetic phase transition.The magnetization as a function of temperature identifies the ferrimagnetic to paramagnetic transition at a Curie temperature of 60 K.Moreover,a Griffiths-like phase is confirmed in a temperature range above T_(C).The compound undergoes a crossover from the first to second-order ferrimagnetic transformation,as evidenced by the Arrott plots,scaling of the universal entropy curve,and field-dependent magnetic entropy change.The maximum of entropy change is 3 J/kg⋅K for ΔH=7 T at T_(C),and a broadening of the entropy peak with increasing magnetic field indicates a field-induced transition above T_(C).The analysis of the magnetic entropy change using the Landau theory reveals the second-order phase transition and indicates that the magnetocaloric properties of CaBaCo_(4)O_(7) are dominated by the magnetoelastic coupling and electron interaction.The corresponding values of refrigerant capacity and relative cooling power are estimated to be 33 J/kg and 42 J/kg,respectively.

Rabi Spectroscopy and Sensitivity of a Floquet Engineered Optical Lattice Clock

We periodically modulate the lattice trapping potential of a ^(87)Sr optical clock to Floquet engineer the clock transition.In the context of atomic gases in lattices,Floquet engineering has been used to shape the dispersion and topology of Bloch quasi-energy bands.Differently from these previous works manipulating the external(spatial)quasi-energies,we target the internal atomic degrees of freedom.We shape Floquet spin quasi-energies and measure their resonance profiles with Rabi spectroscopy.We provide the spectroscopic sensitivity of each band by measuring the Fisher information and show that this is not depleted by the Floquet dynamical modulation.The demonstration that the internal degrees of freedom can be selectively engineered by manipulating the external degrees of freedom inaugurates a novel device with potential applications in metrology,sensing and quantum simulations.

High-performance magnesium-based thermoelectric materials:Progress and challenges

Magnesium-based materials have been regarded as promising candidates for large-scale,high-efficiency thermoelectric applications,owing to their excellent dimensionless figure of merit,high abundance,and low cost.In this review,we comprehensively summarize the recent advances of Mg-based thermoelectrics,including Mg_(2)X(X=Si,Ge,Sn),Mg3(Sb,Bi)_(2),andα-MgAgSb,from both material and device level.Their electrical and thermal transport properties are first elucidated based on the crystallographic characteristics,band structures,and phonon dispersions.We then review the optimization strategies towards higher thermoelectric performance,as well as the device applications of Mg-based thermoelectric materials and the related engineering issues.By highlighting the challenges and possible solutions in the end,this review intends to offer perspectives on the future research work to further enhance the performance of Mg-based materials for practical applications.

Regulating local coordination environment of Mg-Co single atom catalyst for improved direct methanol fuel cell cathode

Fuel cells operated with a reformate fuel such as methanol are promising power systems for portable electronic devices due to their high safety,high energy density and low pollutant emissions.However,several critical issues including methanol crossover effect,CO-tolerance electrode and efficient oxygen reduction electrocatalyst with low or non-platinum usage have to be addressed before the direct methanol fuel cells(DMFCs)become commercially available for industrial application.Here,we report a highly active and selective Mg-Co dualsite oxygen reduction reaction(ORR)single atom catalyst(SAC)with porous N-doped carbon as the substrate.The catalyst exhibits a commercial Pt/C-comparable half-wave potential of 0.806 V(versus the reversible hydrogen electrode)in acid media with good stability.Furthermore,practical DMFCs test achieves a peak power density of over 200 m W cm^(-2)that far exceeds that of commercial Pt/C counterpart(82 m W cm^(-2)).Particularly,the Mg-Co DMFC system runs over 10 h with negligible current loss under 10 M concentration methanol work condition.Experimental results and theoretical calculations reveal that the N atom coordinated by Mg and Co atom exhibits an unconventional d-band-ditto localized p-band and can promote the dissociation of the key intermediate*OOH into*O and*OH,which accounts for the near unity selective 4e-ORR reaction pathway and enhanced ORR activity.In contrast,the N atom in SAC–Co remains inert in the absorption and desorption of*OOH and*OH.This local coordination environment regulation strategy around active sites may promote rational design of high-performance and durable fuel cell cathode electrocatalysts.

Magnetic-Field-Induced Sign Changes of Thermal Expansion in DyCrO_(4)

The anharmonicity of lattice vibration is mainly responsible for the coefficient of thermal expansion(CTE)of materials.External stimuli,such as magnetic and electric fields,thus cannot effectively change the CTE,much less the sign variation from positive to negative or vice versa.In this study,we report significant magnetic field effects on the CTE of zircon-and scheelite-type DyCrO_(4) prepared at ambient and high pressures,respectively.At zero field,the zircon-type DyCrO_(4) exhibits a negative CTE below the ferromagnetic-order temperature of 23 K.With increasing field up to≥1.0 T,however,the sign of the CTE changes from negative to positive.In the scheelite phase,magnetic field can change the initially positive CTE to be negative with a field up to 2.0 T,and then a reentrant positive CTE is induced by enhanced fields≥3.5 T.Both zircon and scheelite phases exhibit considerable magnetostrictive effects with the absolute values as high as~800 ppm at 2 K and 10 T.The strong spin–lattice coupling is discussed to understand the unprecedented sign changes of the CTE caused by applying magnetic fields.The current DyCrO_(4) provides the first example of field-induced sign change of thermal expansion,opening up a way to readily control the thermal expansion beyond the conventional chemical substitution.

Photoinduced Floquet higher-order Weyl semimetal in C_(6) symmetric Dirac semimetals

Topological Dirac semimetals are a parent state from which other exotic topological phases of matter, such as Weyl semimetals and topological insulators, can emerge. In this study, we investigate a Dirac semimetal possessing sixfold rotational symmetry and hosting higher-order topological hinge Fermi arc states, which is irradiated by circularly polarized light. Our findings reveal that circularly polarized light splits each Dirac node into a pair of Weyl nodes due to the breaking of time-reversal symmetry, resulting in the realization of the Weyl semimetal phase. This Weyl semimetal phase exhibits rich boundary states, including two-dimensional surface Fermi arc states and hinge Fermi arc states confined to six hinges.Furthermore, by adjusting the incident direction of the circularly polarized light, we can control the degree of tilt of the resulting Weyl cones, enabling the realization of different types of Weyl semimetals.

Enhancing visible-light-driven NO oxidation through molecular‐level insights of dye-loaded sea sands

Natural minerals,abundant and easily obtained through simple physical processing,offer a cost-effective and environmentally friendly solution for dyeing wastewater disposal and air pollution treatment.This study investigates the photocatalytic removal of NO using natural different types of dyes,loaded on natural sand,under visible light illumination.By examining various coating concentrations of dyes and sand weights,we discovered that sand loaded with Rhodamine B(RhB)exhibits high activity for the photo-oxidation of NO.A combination results of X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),Fourier transform infrared spectroscopy(FTIR)and thermogravimetric(TG)analyses confirm the presence of SiO_(2),CaCO_(3),Al_(2)O_(3)and iron oxides as the main components of the sand.Furthermore,studying RhB-loaded individual components reveals that CaCO_(3)plays a crucial role in enhancing the NO removal rate.Experimental results and theoretical calculations demonstrate the establishment of a directional charge transfer channel from CaCO_(3)to RhB,facilitating the adsorption and activation of molecular NO and O_(2).This work not only promotes the utilization of natural mineral resources but also enriches the fields of environmental photochemistry and semiconductor photocatalysis.

Strongly Coupled Ag/Sn-SnO_(2)Nanosheets Toward CO_(2)Electroreduction to Pure HCOOH Solutions at Ampere‑Level Current

Electrocatalytic reduction of CO_(2) converts intermittent renewable electricity into value-added liquid products with an enticing prospect,but its practical application is hampered due to the lack of high-performance electrocatalysts.Herein,we elaborately design and develop strongly coupled nanosheets composed of Ag nanoparticles and Sn-SnO_(2) grains,designated as Ag/Sn-SnO_(2) nanosheets(NSs),which possess optimized electronic structure,high electrical conductivity,and more accessible sites.As a result,such a catalyst exhibits unprecedented catalytic performance toward CO_(2)-to-formate conversion with near-unity faradaic efficiency(≥90%),ultrahigh partial current density(2,000 mA cm^(−2)),and superior long-term stability(200 mA cm^(−2),200 h),surpassing the reported catalysts of CO_(2) electroreduction to formate.Additionally,in situ attenuated total reflection-infrared spectra combined with theoretical calculations revealed that electron-enriched Sn sites on Ag/Sn-SnO_(2)NSs not only promote the formation of*OCHO and alleviate the energy barriers of*OCHO to*HCOOH,but also impede the desorption of H*.Notably,the Ag/Sn-SnO_(2)NSs as the cathode in a membrane electrode assembly with porous solid electrolyte layer reactor can continuously produce~0.12 M pure HCOOH solution at 100 mA cm^(−2)over 200 h.This work may inspire further development of advanced electrocatalysts and innovative device systems for promoting practical application of producing liquid fuels from CO_(2).

Electrical and thermal transport properties of kagome metals AV3Sb5(A=K,Rb,Cs)

The interplay between lattice geometry,band topology and electronic correlations in the newly discovered kagome compounds AV3Sb5(A=K,Rb,Cs) makes this family a novel playground to investigate emergent quantum phenomena,such as unconventional superconductivity,chiral charge density wave and electronic nematicity.These exotic quantum phases naturally leave nontrivial fingerprints in transport properties of AV3Sb5,both in electrical and thermal channels,which are prominent probes to uncover the underlying mechanisms.In this brief review,we highlight the unusual electrical and thermal transport properties observed in the unconventional charge ordered state of A V3Sb5,including giant anomalous Hall,anomalous Nernst,ambipolar Nernst and anomalous thermal Hall effects.Connections of these anomalous transport properties to time-reversal symmetry breaking,topological and multiband fermiology,as well as electronic nematicity,are also discussed.Finally,a perspective together with challenges of this rapid growing field are given.

An ultrafast carrier dynamics system from oxygen vacancies modified SnO_(2)QDs and Zn_(2)SnO_(4)heterojunction for deeply photocatalytic oxidation of NO

Deeply photocatalytic oxidation of NO-to-NO_(3)holds great promise for alleviating NO_(x) pollution.The major challenge of NO photo-oxidation is the highly in-situ generated NO_(2) concentration,and the formation of unstable nitrate species causes desorption to release NO_(2).In this study,SnO_(2) quantum dots and oxygen vacancies co-modified Zn_(2)SnO_(4)(ZSO-SnO_(2)-OVs)were prepared by a one-step hydrothermal procedure,the NO photo-oxidation was investigated by a combination of solid experimental and theoretical support.Impressively,spectroscopic measurements indicate that fast carrier dynamics can be achieved due to the electron transfer efficiency of ZSO-SnO_(2)-OVs reaching 99.99%,far outperforming the counterpart and previously reported photocatalysts.During NO oxidation,molecular NO/O_(2) and H2O are efficiently adsorbed/activated around OVs and SnO_(2) QDs,respectively.In-situ infrared measurements and calculated electron localized function disclose two main findings:(1)richly electrons enable NO promptly form NOinstead of toxic NO_(2) or NO^(+);(2)the generation of stable and undecomposed bidentate NO_(3)rather than bridging or monodentate one benefits the deep oxidation of NO via shifting reaction sites from O terminals for original ZSO to Sn ones for ZSO-SnO_(2)-OVs.The synergistic action of SnO_(2) QDs and OVs positively contributes to the NO oxidation performance enhancement(60.6%,0.1 g of sample)and high selectivity of NO to NO_(3)(99.2%).Results from this study advance the mechanistic understanding of NO photooxidation and its selectivity to NO_(3)over photocatalysts.

Atom-based power-frequency electric field measurement using the radio-frequency-modulated Rydberg spectroscopy

The radio-frequency modulated electromagnetically induced transparency(EIT) in a ladder three-level system with Rydberg state is studied. Under the influence of a fast radio-frequency field, the EIT peak splits into a series of sidebands.When attaching a power-frequency electric field directly to the fast radio-frequency field, the odd-order sidebands of the Rydberg-EIT oscillate sensitively with the power-frequency field. The oscillation frequency is equal to twice the power frequency;the oscillation amplitude is monotonically increasing with the amplitude of the power-frequency field when the change of Stark-shift is smaller than the radio frequency. Our work paves the way for measurement of power-frequency electric field based on Rydberg atoms.

Chiral edge state coupling theory of transport in quantum anomalous Hall insulators

The quantum anomalous Hall effect is characterized by a quantized Hall resistance with a vanishing longitudinal resistance.Many experiments reported the quantization of the Hall resistance,which is always accompanied by a non-vanishing longitudinal resistance that is several k?.Meanwhile,the non-vanishing longitudinal resistance exhibits a universal exponential decay with the increase in magnetic field.We propose that the coupling of chiral edge states,which has not been properly evaluated in the previous theories,can give rise to the non-vanishing longitudinal resistance.The coupling between the chiral edges states along the opposite boundaries can be assisted by magnetic domains or defects inside the sample bulk,which has been already identified in recent experiments.Our theory provides a potential mechanism to understand the experimental result in both magnetic topological insulator and moirésuperlattice systems.

Unusual magnetic relaxation in a single-molecule magnet with toroidal magnetic moments

We report the synthesis and characterization of a single-molecule magnet composed of triangular clusters of dysprosium ions.The structural study shows that the symmetry changes from one polar point group(mm2)at room temperature to another polar point group(m)at low temperature.Magnetic studies and theory calculations illustrate that the vortex distribution of magnetic dipoles in the triangular dysprosium clusters forms a toroidal magnetic moment.Interestingly,the analysis of AC magnetic susceptibility reveals the coexistence of three distinct magnetic relaxation processes,corresponding to the Raman,Orbach,and QTM relaxation pathways,respectively.The sum of three modified Debye functions is successfully used to describe the multiple relaxation behavior.

Nonadiabatic geometric phase in a doubly driven two-level system

We study theoretically the nonadiabatic geometric phase of a doubly driven two-level system with an additional relative phase between the two driving modes introduced in. It is shown that the time evolution of the system strongly depends on this relative phase. The condition for the system returning to its initial state after a single period is given by the means of the Landau–Zener–Stückelberg–Majorana destructive interference. The nonadiabatic geometric phase accompanying a cyclic evolution is shown to be related to the Stokes phase as well as this relative phase. By controlling the relative phase, the geometric phase can characterize two distinct phases in the adiabatic limit.

Isotype Heterojunction‑Boosted CO_(2) Photoreduction to CO

Photocatalytic conversion of CO_(2) to high-value products plays a crucial role in the global pursuit of carbon–neutral economy.Junction photocatalysts,such as the isotype heterojunctions,offer an ideal paradigm to navigate the photocatalytic CO_(2) reduction reaction(CRR).Herein,we elucidate the behaviors of isotype heterojunctions toward photocatalytic CRR over a representative photocatalyst,g-C_(3)N_(4).Impressively,the isotype heterojunctions possess a significantly higher efficiency for the spatial separation and transfer of photogenerated carriers than the single components.Along with the intrinsically outstanding stability,the isotype heterojunctions exhibit an exceptional and stable activity toward the CO_(2) photoreduction to CO.More importantly,by combining quantitative in situ technique with the first-principles modeling,we elucidate that the enhanced photoinduced charge dynamics promotes the production of key intermediates and thus the whole reaction kinetics.

A new insight into the promoting effects of transition metal phosphides in methanol electrooxidation

The construction of highly active catalysts for methanol oxidation reaction(MOR)is central to direct methanol fuel cells.Tremendous progress has been made in transition metal phosphides(TMPs)based catalysts.However,TMPs would be partially damaged and transformed into new substances(e.g.,Pt-M-P composite,where M represents a second transition metal)during Pt deposition process.This would pose a large obstacle to the cognition of the real promoting effects of TMPs in MOR.Herein,Co_(2)P co-catalysts(Pt-P/Co_(2)P@NPC,where NPC stands for N and P co-doped carbon)and Pt-Co-P composite catalysts(Pt-CoP/NPC)were controllably synthesized.Electrocatalysis tests show that the Pt-Co-P/NPC exhibits superior MOR activity as high as 1016 m A/mg_(Pt),significantly exceeding that of Pt-P/Co_(2)P@NPC(345 m A/mg_(Pt)).This result indicates that the promoting effect is ascribed primarily to the resultant Pt-Co-P composite,in sharply contrast to previous viewpoint that Co_(2)P itself improves the activity.Further mechanistic studies reveal that Pt-Co-P/NPC exhibits much stronger electron interaction and thus manifesting a remarkably weaker CO absorption than Pt-P/Co_(2)P@NPC and Pt/C.Moreover,Pt-Co-P is also more capable of producing oxygen-containing adsorbate and thus accelerating the removal of surface-bonded CO^(*),ultimately boosting the MOR performance.

Doubled Moiré fat bands in double-twisted few-layer graphite

We study the electronic structure of double-twisted few-layer graphite(DTFLG),which consists of three few-layer graphites(FLGs),i.e.,an ABA-stacked graphene multilayer,stacked with two twist angles.We consider two categories of DTFLG,the alternately and chirally twisted cases,according to the rotation direction of the two twist angles.We show that,once the middle FLG of DTFLG is not thinner than the trilayer,both types of DTFLG can remarkably host two pairs of degenerate Moire flat bands(MFBs) at EF,twice that of the magic angle twisted bilayer graphene(TBG).The doubled MFBs of DTFLG lead to a doubled density of states(DOS) at the Fermi level EF,which implies much stronger correlation effects than TBG.The degeneracy of MFBs can be lifted by a perpendicular electric field,and the isolated MFBs have a nonzero valley Chern number.We also reveal the peculiar wave function patterns of the MFB s in DTFLG.Our results establish a new family of Moire systems that have a much higher DOS at EFand thus possibly much stronger correlation effects.

Synthesis-temperature-dependent phase composition manipulation toward high thermoelectric performance in tetrahedrites

Tetrahedrite,an Earth-abundant natural mineral,has attracted extensive research interest because of its excellent thermoelectric performance.Herein,tetrahedrite samples comprising Cu-poor Cu_(12)Sb_(4)S_(13)and Cu-rich Cu_(14)Sb_(4)S_(13)phases have been synthesized using a colloidal method,in which the ratio of two phases is manipulated by controlling the synthesis temperature to improve the thermoelectric perfor-mance.It is found that an ultralow total thermal conductivity of∼0.3 W m^(−1)K^(−1)at 723 K is realized in the sample with a Cu-rich phase fraction of∼50%,which can be attributed to maximized phonon scattering by phase boundaries.As a result,combined with a decent power factor,this sample obtains an optimal zT of 1.15,which is about 85%higher than that of the sample with a Cu-rich phase fraction of∼64%and comparable to zT values of other eco-friendly,abundant Cu-based thermoelectric materials.This work demonstrates an effective synthesis-temperature-dependent phase composition manipulation strategy toward enhanced thermoelectric performance in tetrahedrites.

探索Bi_(2)SeO_(5)的高介电性能:从块体到双层和单层

Bi_(2)SeO_(5)是一种具有优异电绝缘性能的范德华(vdW)层状介电材料,引起了极大关注.然而,目前关于Bi_(2)SeO_(5)的研究主要停留在实验层面,仍然缺乏对其原子级薄膜的介电性能的相关理论认识.本文通过第一性原理计算确定了Bi_(2)SeO_(5)的介电性能,发现其块体、双层和单层均具有超高平均介电常数(εr>20).研究表明,单层Bi_(2)SeO_(5)与双层Bi_(2)O_(2)Se之间的导带和价带能量偏移量均大于1 eV,表明单层Bi_(2)SeO_(5)依然可作为原子薄Bi_(2)O_(2)Se的良好介电层.此外,不同于h-BN或其他2D vdW绝缘体,Bi_(2)SeO_(5)的εr由其离子部分主导,且随着厚度的减小几乎保持不变.计算发现,单层Bi_(2)SeO_(5)的等效氧化层厚度可薄至0.3 n m,且单层Bi_(2)SeO_(5)在拉伸或压缩应变达到6%时均能保持高介电常数,这极大地促进了它与各种二维半导体的集成.本工作证明单层Bi_(2)SeO_(5)可以作为高性能二维电子器件良好的封装和介电层.