Switching O-O bond formation mechanism between WNA and I2M pathways by modifying the Ru-bda backbone ligands of water-oxidation catalysts

Understanding the seven coordination and O-O coupling pathway of the distinguished Ru-bda catalysts is essential for the development of next generation efficient water-oxidation catalysts based on earthabundant metals.This work reports the synthesis,characterization and catalytic properties of a monomeric ruthenium catalyst Ru-bnda(H2 bnda=2,2’-bi(nicotinic acid)-6,6’-dicarboxylic acid)featuring steric hindrance and enhanced hydrophilicity on the backbone.Combining experimental evidence with systematic density functional theory calculations on the Ru-bnda and related catalysts Ru-bda(H_(2)bda=2,2’-bipyridine-6,6’-dicarboxylic acid),Ru-pda(H_(2)pda=1,10-phenanthroline-2,9-dicarboxylic acid),and Ru-biqa(H_(2)biqa=(1,1’-biisoquinoline)-3,3’-dicarboxylic acid),we emphasized that seven coordination clearly determines presence of Ru^(Ⅴ)=O with high spin density on the ORu^(Ⅴ)=O atom,i.e.oxo with radical properties,which is one of the necessary conditions for reacting through the O-O coupling pathway.However,an additional factor to make the condition sufficient is the favorable intermolecular faceto-face interaction for the generation of the pre-reactive[Ru^(Ⅴ)=O…O=Ru^(Ⅴ)],which may be significantly influenced by the secondary coordination environments.This work provides a new understanding of the structure-activity relationship of water-oxidation catalysts and their potential to adopt I2M pathway for O-O bond formation.

Doping effect on the structure and physical properties of quasi-one-dimensional compounds Ba_(9)Co_(3)(Se_(1−x)S_(x))_(15)(x=0-0.2)

A series of samples of Ba_(9)Co_(3)(Se_(1−x)S_(x))_(15)(x=0,0.05,0.1,0.15,0.2)with quasi-one-dimensional(1D)structure were successfully synthesized under high-temperature and high-pressure conditions.The influence of partial substitution of S for Se on the structure,electronic transport,and magnetic properties of Ba_(9)Co_(3)(Se_(1−x)S_(x))_(15) has been investigated in detail.The x-ray diffraction data shows that the lattice constant decreases linearly with increasing S-doping level,which follows the Vegrad’s law.The doped S atoms preferentially occupy the site of Se atoms in CoSe6 octahedron.Physical properties measurements indicate that all the samples of Ba_(9)Co_(3)(Se_(1−x)S_(x))_(15) are semiconducting and display spin glass behavior.As the replacement of Se by smaller size S,although the inter-chain distance decreases,the electronic hopping between CoSe/S6 chains is weakened and leads to an increase of band gap from 0.75 eV to 0.86 eV,since the S-3p electrons are more localized than Se-4p ones.Ba_(9)Co_(3)(Se_(1−x)S_(x))_(15) exhibits 1D conducting chain characteristic.

Erratum:Flat Band and Z_(2) Topology of Kagome Metal CsTi_(3)Bi_(5)[Chin.Phys.Lett.40,037102(2023)]

In our most recently published article,[1]an important reference[2]predicting CsTi_(3)Bi_(5) is missing and should be added,along with Ref.[3](originally Ref.[28]),to the introduction section.

Flat Band and Z_(2)Topology of Kagome Metal CsTi_(3)Bi_(5)

The simple kagome-lattice band structure possesses Dirac cones,flat band,and saddle point with van Hove singularities in the electronic density of states,facilitating the emergence of various electronic orders.Here we report a titanium-based kagome metal CsTi_(3)Bi_(5)where titanium atoms form a kagome network,resembling its isostructural compound CsV_3Sb_5.Thermodynamic properties including the magnetization,resistance,and heat capacity reveal the conventional Fermi liquid behavior in the kagome metal CsTi_(3)Bi_(5)and no signature of superconducting or charge density wave(CDW)transition anomaly down to 85 m K.Systematic angle-resolved photoemission spectroscopy measurements reveal multiple bands crossing the Fermi level,consistent with the first-principles calculations.The flat band formed by the destructive interference of hopping in the kagome lattice is observed directly.Compared to Cs V_(3)Sb_(5),the van Hove singularities are pushed far away above the Fermi level in CsTi_(3)Bi_(5),in line with the absence of CDW.Furthermore,the first-principles calculations identify the nontrivial Z_(2)topological properties for those bands crossing the Fermi level,accompanied by several local band inversions.Our results suppose CsTi_(3)Bi_(5)as a complementary platform to explore the superconductivity and nontrivial band topology.

Ultrafast photoemission electron microscopy:A multidimensional probe of nonequilibrium physics

Exploring the realms of physics that extend beyond thermal equilibrium has emerged as a crucial branch of condensed matter physics research.It aims to unravel the intricate processes involving the excitations,interactions,and annihilations of quasi-and many-body particles,and ultimately to achieve the manipulation and engineering of exotic non-equilibrium quantum phases on the ultrasmall and ultrafast spatiotemporal scales.Given the inherent complexities arising from many-body dynamics,it therefore seeks a technique that has efficient and diverse detection degrees of freedom to study the underlying physics.By combining high-power femtosecond lasers with real-or momentum-space photoemission electron microscopy(PEEM),imaging excited state phenomena from multiple perspectives,including time,real space,energy,momentum,and spin,can be conveniently achieved,making it a unique technique in studying physics out of equilibrium.In this context,we overview the working principle and technical advances of the PEEM apparatus and the related laser systems,and survey key excited-state phenomena probed through this surface-sensitive methodology,including the ultrafast dynamics of electrons,excitons,plasmons,spins,etc.,in materials ranging from bulk and nano-structured metals and semiconductors to low-dimensional quantum materials.Through this review,one can further envision that time-resolved PEEM will open new avenues for investigating a variety of classical and quantum phenomena in a multidimensional parameter space,offering unprecedented and comprehensive insights into important questions in the field of condensed matter physics.

Towards high-performance lithium metal anodes via the modification of solid electrolyte interphases

Li metal has been regarded as one of the most promising anodes for high-energy-density storage systems due to its high theoretical capacity and lowest electrochemical potential.Unfortunately,an unstable and non-uniform solid electrolyte interphase(SEI)deriving from the spontaneous reaction between Li metal anode and electrolyte causes uneven Li deposition,resulting in the growth of Li dendrites and low Coulombic efficiency,which have greatly hindered the practical application of Li metal batteries.Thus,the construction of a stable SEI is an effective approach to suppress the growth of Li dendrites and enhance the electrochemical performances of Li metal anode.In this review,we firstly introduce the formation process of inferior SEI of Li metal anode and the corresponding challenges caused by the unstable SEI.Next,recent progresses to modify SEI layer through the regulation of electrolyte compositions and exsitu protective coating are summarized.Finally,the remained issues,challenges,and perspectives are also proposed on the basis of current research status and progress.

Revealing the working mechanism of a multi-functional block copolymer binder for lithium-sulfur batteries

The lithium-sulfur(Li-S)battery is one of the most promising substitutes for current energy storage systems because of its low cost,high theoretical capacity,and high energy density.However,the high solubility of intermediate products(i.e.,lithium polysulfides)and the resultant shuttle effect lead to rapidly fading capacity and a low coulombic efficiency,which hinder the practical application of Li-S batteries.In this study,block copolymers are constructed with both an ethylene oxide unit and a styrene unit and then used as binders for Li-S batteries.Electrochemical performance improvements are attributed to the synergistic effects contributed by the different units of the block copolymer.The ethylene oxide unit traps polysulfide,which bonds strongly with the intermediate lithium polysulfide,and enhances the transport of lithium ions to reach high capacity.Meanwhile,the styrene unit maintains cathode integrity by improving the mechanical properties and elasticity of the constructed block copolymer to accommodate the large volume changes.By enabling multiple functions via different units in the polymer chain,high sulfur utilization is achieved,polysulfide diffusion is confined,and the shuttle effect is suppressed during the cycle life of Li-S batteries,as revealed by operando ultraviolet-visible spectroscopy and S Kedge X-ray absorption spectroscopy.

Self-assembled donor-acceptor hole contacts for inverted perovskite solar cells with an efficiency approaching 22%: The impact of anchoring groups

Self-assembled molecules(SAMs) have shown great potential in replacing bulk charge selective contact layers in high-performance perovskite solar cells(PSCs) due to their low material consumption and simple processing. Herein, we design and synthesize a series of donor-acceptor(D-A) type SAMs(MPA-BTCA, MPA-BT-BA, and MPA-BT-RA, where MPA is 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline;BT is benzo[c][1,2,5]-thiadiazole;CA is 2-cyanoacrylic acid, BA is benzoic acid, RA is rhodanine-3-propionic acid) with distinct anchoring groups, which show dramatically different properties. MPA-BTCA with CA anchoring groups exhibited stronger dipole moments and formed a homogeneous monolayer on the indium tin oxide(ITO) surface by adopting an upstanding self-assembling mode. However, the MPA-BT-RA molecules tend to aggregate severely in solid state due to the sp~3 hybridization of the carbon atom on the RA group, which is not favorable for achieving a long-range ordered self-assembled layer.Consequently, benefiting from high dipole moment, as well as dense and uniform self-assembled film,the device based on MPA-BT-CA yielded a remarkable power conversion efficiency(PCE) of 21.81%.Encouragingly, an impressive PCE approaching 20% can still be obtained for the MPA-BT-CA-based PSCs as the device area is increased to 0.80 cm^(2). Our work sheds light on the design principles for developing hole selecting SAMs, which will pave a way for realizing highly efficient, flexible, and large-area PSCs.

Pressure Driven Structural Evolutions of 0.935(Na0.5Bi0.5)TiO_(3)-0.065BaTiO_(3)Lead-Free Ferroelectric Single Crystal through Raman Spectroscopy

Pressure evolution of local structure and vibrational dynamics of the perovskite-type relaxor ferroelectric single crystal of 0.935(Na0.5Bi0.5)TiO3-0.065BaTiO3(NBT-6.5BT)is systematically investigated via in situ Raman spectroscopy.The pressure dependence of phonon modes up to 30GPa reveals two characteristic pressures:one is at around 4.6GPa which corresponds to the rhombohedral-to-tetragonal phase transition,showing that the pressure strongly suppresses the coupling between the off-centered A-and B-site cations;the other structural transition involving the oxygen octahedral tilt and vibration occurs at pressure∼13–15GPa with certain degree of order-disorder transition,evidenced by the abnormal changes of intensity and FWHM in Raman spectrum.

Optimization of solvent swelling for efficient organic solar cells via sequential deposition

Compared to bulk heterojunction(BHJ)organic solar cells(OSCs)prepared by the blend casting in“one step process”,sequential deposition(SD)processed OSCs can realize an ideal profile of vertical component distribution due to the swelling of polymer films.Herein,we did trials on several kinds of second solvents for swelling the polymer layer,and investigated the packing structure and morphology of the swollen films and the performance of the resulting devices.We found that an optimized morphology can be achieved by solvent swelling while using orthodichlorobenzene(o-DCB)as the second layer processing-solvent,with polymer donor PffBT-3 as bottom layer,PC71BM as top layer and bicontinuous networks in the middle.Such solvent swelling process also makes the SD method exempt from thermal annealing treatment.The device based on SD yields a power conversion effi-ciency(PCE)up to 8.7%without any post-treatment,outperforming those from the devices based on SD using other solvents and that(7.06%)from BHJ device,respectively.We also extended the use of this approach to allpolymer blend system,and successfully improved the efficiency from 4.72%(chloroform)to 9.35%(o-DCB),which is among the highest PCEs in all-polymer-based OSCs fabricated with SD method.The results demonstrate that the swelling of the polymer by the second layer solvent is a necessity for SD,paving the way towards additivefree high-performance OSCs.

Multiple surface states,nontrivial band topology,and antiferromagnetism in GdAuAl_(4)Ge_(2)

Magnetic topological states of matter provide a fertile playground for emerging topological physics and phenomena.The current main focus is on materials whose magnetism stems from 3d magnetic transition elements,e.g.,MnBi_(2)Te_(4),Fe_(3)Sn_(2),and Co_(3)Sn_(2)S_(2).In contrast,topological materials with the magnetism from rare earth elements remain largely unexplored.Here we report rare earth antiferromagnet GdAuAl_(4)Ge_(2)as a candidate magnetic topological metal.Angle resolved photoemission spectroscopy(ARPES)and first-principles calculations have revealed multiple bulk bands crossing the Fermi level and pairs of low energy surface states.According to the parity and Wannier charge center analyses,these bulk bands possess nontrivial Z2 topology,establishing a strong topological insulator state in the nonmagnetic phase.Furthermore,the surface band pairs exhibit strong termination dependence which provides insight into their origin.Our results suggest GdAuAl_(4)Ge_(2)as a rare earth platform to explore the interplay between band topology,magnetism and f electron correlation,calling for further study targeting on its magnetic structure,magnetic topology state,transport behavior,and microscopic properties.

Formation of the structure-Ⅱgas hydrate from low-concentration propane mixed with methane

It has been recognized that a small amount of propane mixed with methane can change greatly in not only the thermodynamics but also the structural properties of gas hydrate.However,its mechanism is still not well understood yet.In this research,structure-Ⅱ(sⅡ)hydrate is synthesized using a methanepropane gas mixture with an initial mole ratio of 99:1,and it is found that large(5~(12)6~4)cages are cooccupied by multiple gases based on the rigid structure analysis of neutron diffraction data.The first principles calculation and molecular dynamics simulation are conducted to uncover the molecular mechanism for sⅡmethane-propane hydrate formation,revealing that the presence of propane inhibits the formation of structure-Ⅰ(sⅠ)hydrate but promotes sⅡhydrate formation.The results help to understand the accumulation mechanism of natural gas hydrate and benefit to optimize the condition for gas storage and transportation in hydrate form.

Synthesis of Polycrystalline Diamond Compact with Selenium:Discovery of a New Se–C Compound

Sintering of polycrystalline diamond with selenium was investigated under pressure of 6.5-10.5 GPa at a constant temperature of 1850℃.A new carbon-selenium compound with a most plausible chemical formula of SeC and a WC-type hexagonal structure(space group P6m2)has been discovered in the recovered samples sintered at 10.5 GPa and 1850℃.Refined lattice parameters are as follows:a=2.9277(4)A,c=2.8620(4)A,V=21.245(4)A^3.The diamond compacts hot-pressed at 10.5 GPa have excellent mechanical properties with a Vickers hardness of about 68 GPa at a loading force of 19.6 N.Diamond intergrowths observed in these samples may have benefited from the catalytic effects of Se/SeC on the nucleation and crystal growth of diamond.

Introduction of the 1st Asia-Pacific Geophysics Student Conference(APGSC 2020)

The Asia-Pacific Geophysics Student Conference(APGSC 2020)is the first student-led and student-organized international geophysics conference in the Asia-Pacific region.The theme of APGSC is"Bridging the Gap between Exploration and Solid-Earth Geophysics".This conference is designed to provide a platform for gathering students with different geophysical backgrounds to exchange ideas,show research results,and explore the frontiers of geophysics and related fields.Students could better understand current and future developments of geophysics and build a bridge between exploration and solid-earth geophysics.The 1st Asia Pacific Geophysical Student Conference(APGSC 2020)is successfully held online on September 6-9,2020 Beijing time.This conference is hosted by the University of Science and Technology of China(USTC)and the Society of Exploration Geophysicists(SEG).More than 30 universities and scientific research institutions at home and abroad give strong support as co-organizers.The academic committee of the conference is composed of more than 50 experts and scholars.

Endomembrane-biased dimerization of ABCG16 and ABCG25 transporters determines their substrate selectivity in ABA-regulated plant growth and stress responses

ATP-binding cassette(ABC)transporters are integral membrane proteins that have evolved diverse func-tions fulfilled via the transport of various substrates.In Arabidopsis,the G subfamily of ABC proteins is particularly abundant and participates in multiple signaling pathways during plant development and stress responses.In this study,we revealed that two Arabidopsis ABCG transporters,ABCG16 and ABCG25,engage in ABA-mediated stress responses and early plant growth through endomembrane-specific dimerization-coupled transport of ABA and ABA-glucosyl ester(ABA-GE),respectively.We first revealed that ABCG16 contributes to osmotic stress tolerance via ABA signaling.More specifically,ABCG16 induces cellular ABA efflux in both yeast and plant cells.Using FRET analysis,we showed that ABCG16 forms oblig-atory homodimers for ABA export activity and that the plasma membrane-resident ABCG16 homodimers specifically respond to ABA,undergoing notable conformational changes.Furthermore,we demonstrated that ABCG16 heterodimerizes with ABCG25 at the endoplasmic reticulum(ER)membrane and facilitates the ER entry of ABA-GE in both Arabidopsis and tobacco cells.The specific responsiveness of the ABCG16-ABCG25 heterodimer to ABA-GE and the superior growth of their double mutant support an inhib-itory role of these twoABCGs in early seedling establishment via regulation of ABA-GE translocation across the ER membrane.Our endomembrane-specific analysis of the FRET signals derived from the homo-or heterodimerized ABcG complexes allowed us to link endomembrane-biased dimerization to the transloca-tion of distinct substrates by ABcG transporters,providing a prototypic framework for understanding the omnipotence of ABcG transporters in plant development and stress responses.

Bimetallic Metal-Organic Framework with High-Adsorption Capacity toward Lithium Polysulfides for Lithium–sulfur Batteries

The practical application of Li-S batteries is largely impeded by the“shuttle effect”generated at the cathode which results in a short life cycle of the battery.To address this issue,this work discloses a bimetallic metal-organic framework(MOF)as a sulfur host material based on Al-MOF,commonly called(Al)MIL-53.To obtain a high-adsorption capacity to lithium polysulfides(Li_(2)S_(x),4≤x≤8),we present an effective strategy to incorporate sulfiphilic metal ion(Cu^(2+))with high-binding energy to Li_(2)S_(x) into the framework.Through a one-step hydrothermal method,Cu^(2+) is homogeneously dispersed in Al-MOF,producing a bimetallic Al/Cu-MOF as advanced cathode material.The macroscopic Li2S4 solution permeation test indicates that the Al/Cu-MOF has better adsorption capacity to lithium polysulfides than monometallic Al-MOF.The sulfur-transfusing process is executed via a melt-diffusion method to obtain the sulfur-containing Al/CuMOF(Al/Cu-MOF-S).The assembled Li-S batteries with Al/Cu-MOF-S yield improved cyclic performance,much better than that of monometallic AlMOF as sulfur host.It is shown that chemical immobilization is an effective method for polysulfide adsorption than physical confinement and the bimetallic Al/Cu-MOF,formed by incorporation of sulfiphilic Cu^(2+) into porous MOF,will provide a novel and powerful approach for efficient sulfur host materials.

A three-dimensional crosslinked chitosan sulfate network binder for high-performance Li-S batteries

Poor cycling performance caused by the shuttle effect of polysulfides is the main obstacle in the development of advanced lithium-sulfur(Li-S)batteries.Functional polymer binders with polar groups can effectively adsorb polysulfides chemically,thereby suppressing the shuttle effect.Herein,a robust three-dimensional crosslinked polymer network,which demonstrates excellent mechanical property and strong affinity for polysulfides,is prepared by the aldimine condensation and coordination reactions.The crosslinked chitosan sulfate network(CCSN)significantly enhances the cycling performance and rate capability of the sulfur cathode.The CCSN-based sulfur cathode exhibits a high initial discharge capacity of 824 m Ah g^(-1) with only 0.082%average capacity loss per cycle at 1 C.At a high rate of 4 C,the cathode exhibits a high capacity retention of 84.8%after 300 cycles.Moreover,the CCSN-based sulfur cathode exhibits an excellent cycling performance at a high sulfur loading of 2.5 mg cm^(-2),which indicates the excellent mechanical strength and binding performance of the CCSN binder for high-energy density Li-S batteries.This study demonstrates a viable approach for developing high-performance Li-S batteries for practical application.

Printing photovoltaics by electrospray

Solution processible photovoltaics(PV)are poised to play an important role in scalable manufacturing of low-cost solar cells.Electrospray is uniquely suited for fabricating PVs due to its several desirable characteristics of an ideal manufacturing process such as compatibility with roll-to-roll production processes,tunability and uniformity of droplet size,capability of operating at atmospheric pressure,and negligible material waste and nano structures.This review begins with an introduction of the fundamentals and unique properties of electrospray.We put emphasis on the evaporation time and residence time that jointly affect the deposition outcome.Then we review the efforts of electrospray printing polymer solar cells,perovskite solar cells,and dye sensitized solar cells.Collectively,these results demonstrate the advantages of electrospray for solution processed PV.Electrospray has also exhibited the capability of producing uniform films as well as nanostructured and even multiscale films.So far,the electrospray has been found to improve active layer morphology,and create devices with efficiencies comparable with that of spin-coating.Finally,we discuss challenges and research opportunities that enable electrospray to become a mainstream technique for industrial scale production.

Interplay of phytohormones and epigenetic regulation:A recipe for plant development and plasticity

Both phytohormone signaling and epigenetic mechanisms have long been known to play crucial roles in plant development and plasticity in response to ambient stimuli.Indeed,diverse signaling pathways mediated by phytohormones and epigenetic processes integrate multiple upstream signals to regulate various plant traits.Emerging evidence indicates that phytohormones and epigenetic processes interact at multiple levels.In this review,we summarize the current knowledge of the interplay between phytohormones and epigenetic processes from the perspective of phytohormone biology.We also review chemical regulators used in epigenetic studies and propose strategies for developing novel regulators using multidisciplinary approaches.

Asymmetric Access of γ-Amino Acids and γ-Amino Phosphonic Acid Derivatives via Copper-Catalyzed Enantioselective and Regioselective Hydroamination

γ-Aminobutyric acid is a major inhibitory neurotransmitter in the mammalian central nervous system that plays a substantial role in brain disorders.γ-Amino phosphonic acid is a unique surrogate of both natural and unnatural γ-amino acid.Because of their unique biological activity,γ-amino acid and γ-amino phosphonic acid derivatives have attracted considerable attention.However,an efficient and straightforward method for constructing chiral γ-substituted-γ-amino acid and γ-amino phosphonic acid derivatives remains a long-standing challenge.Herein,a highly efficient,versatile,and universal Cucatalyzed asymmetric hydroamination of cinnamyl esters,cinnamyl phosphonates,and cinnamyl phosphine oxides is presented for accessing γ-amino acid andγ-amino phosphonic acid derivatives in good yields with high levels of enantiocontrol and regioselectivity.