草业科学的发展历程、学科体系及新时期的使命任务

草业科学,是研究草类植物与草地属性、功能及其合理利用的学科。草业科学是一门年轻的学科,整合了国际上草原学、饲草学、草地农业科学的学科特点,在任继周草地农业生态系统理论的基础上发展起来的。我国已经建立了具有中国特色的草业科学学科体系,根据学科的内涵和发展,目前设置了草原学、饲草学、草坪学、草地保护学和草业经营学5个二级学科。本文在简要总结草业科学发展历程的基础上,结合本世纪在草地农业生态系统多功能性、多服务性、以及多功能管理方面的新进展,建议增列草地农业系统学二级学科。新时期草业面临重大的国家需求:确保饲草安全,才能实现粮食安全;树立大食物观,大力发展草地农业,在多元化食物供给体系中发挥作用;立足国家生态屏障建设,在草地保护和修复事业中发挥支撑作用。本文进一步总结了这些需求背后的科技难题。国家的重大需求,对草业科学和草业人,既是机遇,也是挑战,更是使命。

Advances of Synergistic Electrocatalysis Between Single Atoms and Nanoparticles/Clusters

Combining single atoms with clusters or nanoparticles is an emerging tactic to design efficient electrocatalysts.Both synergy effect and high atomic utilization of active sites in the composite catalysts result in enhanced electrocatalytic performance,simultaneously provide a radical analysis of the interrelationship between structure and activity.In this review,the recent advances of single-atomic site catalysts coupled with clusters or nanoparticles are emphasized.Firstly,the synthetic strategies,characterization,dynamics and types of single atoms coupled with clusters/nanoparticles are introduced,and then the key factors controlling the structure of the composite catalysts are discussed.Next,several clean energy catalytic reactions performed over the synergistic composite catalysts are illustrated.Eventually,the encountering challenges and recommendations for the future advancement of synergistic structure in energy-transformation electrocatalysis are outlined.

Defect and Doping Co‑Engineered Non‑Metal Nanocarbon ORR Electrocatalyst

Exploring low-cost and earth-abundant oxygen reduction reaction(ORR)electrocatalyst is essential for fuel cells and metal–air batteries.Among them,non-metal nanocarbon with multiple advantages of low cost,abundance,high conductivity,good durability,and competitive activity has attracted intense interest in recent years.The enhanced ORR activities of the nanocarbons are normally thought to originate from heteroatom(e.g.,N,B,P,or S)doping or various induced defects.However,in practice,carbon-based materials usually contain both dopants and defects.In this regard,in terms of the co-engineering of heteroatom doping and defect inducing,we present an overview of recent advances in developing non-metal carbon-based electrocatalysts for the ORR.The characteristics,ORR performance,and the related mechanism of these functionalized nanocarbons by heteroatom doping,defect inducing,and in particular their synergistic promotion effect are emphatically analyzed and discussed.Finally,the current issues and perspectives in developing carbon-based electrocatalysts from both of heteroatom doping and defect engineering are proposed.This review will be beneficial for the rational design and manufacturing of highly efficient carbon-based materials for electrocatalysis.

Well-ordered layered LiNi0.8Co0.1Mn0.1O2 submicron sphere with fast electrochemical kinetics for cathodic lithium storage

Nickel-rich layered oxides have drawn sustainable attentions for lithium ion batteries owing to their higher theoretical capacities and lower cost.However,nickel-rich layered oxides also have exposed several defects for commercial application,such as uncontrollable ordered layered structure,which leads to higher energy barrier for Li+diffusion.In addition,suffering from structural mutability,the bulk nickelrich cathode materials likely trigger overall volumetric variation and intergranular cracks,thus obstructing the lithium ion diffusion path and shortening the service life of the whole device.Herein,we report wellordered layered Li Ni0.8Co0.1Mn0.1O2 submicron spheroidal particles via an optimized co-precipitation and investigated as LIBs cathodes for high-performance lithium storage.The as-fabricated Li Ni0.8Co0.1Mn0.1O2 delivers high initial capacity of 228 mAh g–1,remarkable energy density of 866 Wh kg–1,rapid Li ion diffusion coefficient(10–9cm2s–1)and low voltage decay.The remarkable electrochemical performance should be ascribed to the well-ordered layered structure and uniform submicron spheroidal particles,which enhance the structural stability and ameliorate strain relaxation via reducing the parcel size and shortening Li-ion diffusion distance.This work anticipatorily provides an inspiration to better design particle morphology for structural stability and rate capability in electrochemistry energy storage devices.

Exploring the interconnectivity of biomimetic hierarchical porous Mg scaffolds for bone tissue engineering:Effects of pore size distribution on mechanical properties,degradation behavior and cell migration ability

Interconnectivity is the key characteristic of bone tissue engineering scaffold modulating cell migration,blood vessels invasion and transport of nutrient and waste.However,efforts and understanding of the interconnectivity of porous Mg is limited due to the diverse architectures of pore struts and pore size distribution of Mg scaffold systems.In this work,biomimetic hierarchical porous Mg scaffolds with tailored interconnectivity as well as pore size distribution were prepared by template replication of infiltration casting.Mg scaffold with better interconnectivity showed lower mechanical strength.Enlarging interconnected pores would enhance the interconnectivity of the whole scaffold and reduce the change of ion concentration,pH value and osmolality of the degradation microenvironment due to the lower specific surface area.Nevertheless,the degradation rates of five tested Mg scaffolds were no different because of the same geometry of strut unit.Direct cell culture and evaluation of cell density at both sides of four typical Mg scaffolds indicated that cell migration through hierarchical porous Mg scaffolds could be enhanced by not only bigger interconnected pore size but also larger main pore size.In summary,design of interconnectivity in terms of pore size distribution could regulate mechanical strength,microenvironment in cell culture condition and cell migration potential,and beyond that it shows great potential for personalized therapy which could facilitate the regeneration process.

Ultrafine Ni-B nanoparticles for efficient hydrogen evolution reaction

The search for active,stable,and cost-effective electrocatalysts for hydrogen evolution reaction(HER)is desirable,but it remains a great challenge in the overall water splitting.Here,we report the synthesis of nickel boron nanoparticles supported on Vulcan carbon(Ni-B)via a simple,yet scalable,two-step chemical reduction–annealing strategy.The results of the electrochemical measurements suggest that the overpotentials of Ni-B-400 are 114 and 215 mV(in 1 mol L^–1 KOH)at current densities of 10 and 40 mA cm^?2,respectively,indicating an exceedingly good electrocatalytic activity in the HER.More importantly,Ni-B maintains a current density of 7.6 mA cm^-2 at an overpotential of 0.15 V for 20 h in the durability test.The excellent HER activity of Ni-B-400 is derived from the small particle size and the expanded lattice of Ni,which can optimize the hydrogen absorption energy and enhance the electrocatalytic properties.

Element doping induced microstructural engineering enhancing the lithium storage performance of high-nickel layered cathodes

The high-nickel layered cathodes Li[Ni_(x)Co_(y)Mn_(1-x-y)]O_(2)(x≥0.8)with high specific capacity and long cycle life are considered as prospective cathodes for lithium-ion batteries.However,the microcrack formation and poor structural stability give rise to inferior rate performance and undesirable cycling life.Herein,we propose a dual modification strategy combining primary particle structure design and element doping to modify Li[Ni_(0.95)Co_(0.025)Mn_(0.025)]O_(2) cathode by tungsten and fluorine co-doped(W-F-NCM95).The doping of W can convert the microstructure of primary particles to the unique rod-like shape,which is beneficial to enhance the reversibility of phase transition and alleviate the generation of microcracks.F doping is conducive to alleviating the surface side reactions.Thus,due to the synergistic effect of W,F codoping,the obtained W-F-NCM95 cathodes deliver a high initial capacity of 236.1 mA h g^(-1) at 0.1 C and superior capacity retention of 88.7%over 100 cycles at 0.5 C.Moreover,the capacity still maintains73.8%after 500 cycles at 0.5 C and the texture of primary particle is intact.This work provides an available strategy by W and F co-doping to enhance the electrochemistry performance of high-nickel cathodes for practical application.

Boosting alkaline hydrogen electrooxidation on an unconventional fcc-Ru polycrystal

Precisely controlling the crystalline phase structure and exposed facets at the atomic level opens up a new avenue for efficient catalyst design.Along this line,we report an unconventional face-centered cubic(fcc)Ru with twinned structure and stacking-fault defects as a competent electrocatalyst towards alkaline hydrogen oxidation reaction(HOR),which is now a major obstacle for the commercialization of anion exchange membrane fuel cells(AEMFC).With conventional hexagonal close packing(hcp)Ru as the counterpart,a novel scope from the phase-engineering is introduced to identify the activity origin and provide fundamental understanding of the sluggish HOR kinetics in alkaline medium.Systematic electrochemical analysis assisted by deconvoluting the hydrogen(H)desorption peaks indicates the superior performance of fcc Ru origins from the structure defects and higher proportion of the most active sites.DFT calculations,together with CO-stripping voltammograns further corroborate the stronger hydroxyl species(OH^(*))affinity lead to the higher activity on these sites.Meanwhile,it also demonstrates the H^(*)adsorption/desorption on polycrystalline Ru among the conventional"hydrogen region"is accompanied by the surface bound OH^(*)in alkaline medium,which is of great significance for subsequent alkaline HOR exploration and catalyst design.

Glucose-derived carbon sphere supported CoP as efficient and stable electrocatalysts for hydrogen evolution reaction

Glucose-derived carbon sphere supported cobalt phosphide nanoparticles（Co P/C） were synthesized via a concise two-step method. The electrochemical measurement results indicate that the Co P/C prepared at 900 ℃ presents excellent electrocatalytic performance for hydrogen evolution reaction（HER）. The overpotential at a current density of 10 m A cmis 108 and 163 mV in 0.5 M HSOand 1 M KOH, respectively, and maintains its electrocatalytic durability for at least 10 h. This work supplies a new field to challenge the construction of electrocatalysts for HER through using cost-effective carbon supported transition metal phosphides.

High-entropy L1_(2)-Pt(FeCoNiCuZn)_(3) intermetallics for ultrastable oxygen reduction reaction

Enhancing the stability of Pt-based electrocatalysts for the sluggish cathodic oxygen reduction reaction(ORR)is critical for proton exchange membrane fuel cells(PEMFCs).Herein,high-entropy intermetallic(HEI)L1_(2)-Pt(FeCoNiCuZn)3is designed for durable ORR catalysis.Benefiting from the unique HEI structure and the enhanced intermetallic phase stability,Pt(FeCoNiCuZn)3/C nanoparticles demonstrate significantly improved stability over Pt/C and PtCu_(3)/C catalysts.The Pt(FeCoNiCuZn)3/C exhibits a negligible decay of the half-wave potential during 30,000 potential cycles from 0.6 to 1.0 V,whereas Pt/C and PtCu_(3)/C are negatively shifted by 46 and 36 m V,respectively.Even after 10,000 cycles at potential up to 1.5 V,the mass activity of Pt(FeCoNiCuZn)3/C still shows~70%retention.As evidenced by the structural characterizations,the HEI structure of Pt(FeCoNiCuZn)3/C is well maintained,while PtCu_(3)/C nanoparticles undergo severe Cu leaching and particle growth.In addition,when assembled Pt(FeCoNiCuZn)3/C as the cathode in high-temperature PEMFC of 160℃,the H_(2)-O_(2)fuel cell delivers almost no degradation even after operating for 150 h,demonstrating the potential for fuel cell applications.This work provides a facile design strategy for the development of high-performance ultrastable electrocatalysts.

Recent Advances of Electrocatalyst and Cell Design for Hydrogen Peroxide Production

Electrochemical synthesis of H_(2)O_(2) via a selective two-electron oxygen reduction reaction has emerged as an attractive alternative to the current energy-consuming anthraquinone process. Herein, the progress on electrocatalysts for H_(2)O_(2) generation, including noble metal, transition metalbased, and carbon-based materials, is summarized. At first, the design strategies employed to obtain electrocatalysts with high electroactivity and high selectivity are highlighted. Then, the critical roles of the geometry of the electrodes and the type of reactor in striking a balance to boost the H_(2)O_(2) selectivity and reaction rate are systematically discussed. After that, a potential strategy to combine the complementary properties of the catalysts and the reactor for optimal selectivity and overall yield is illustrated. Finally, the remaining challenges and promising opportunities for highefficient H_(2)O_(2) electrochemical production are highlighted for future studies.

Stationary response of stochastic viscoelastic system with the right unilateral nonzero offset barrier impacts

The stationary response of viscoelastic dynamical system with the right unilateral nonzero offset barrier impacts subjected to stochastic excitations is investigated. First, the viscoelastic force is approximately treated as equivalent terms associated with effects. Then, the free vibro-impact(VI) system is absorbed to describe the periodic motion without impacts and quasi-periodic motion with impacts based upon the level of system energy. The stochastic averaging of energy envelope(SAEE) is adopted to seek the stationary probability density functions(PDFs). The detailed theoretical results for Van der Pol viscoelastic VI system with the right unilateral nonzero offset barrier are solved to demonstrate the important effects of the viscoelastic damping and nonzero rigid barrier impacts condition. Monte Carlo(MC) simulation is also performed to verify the reliability of the suggested approach. The stochastic P-bifurcation caused by certain system parameters is further explored. The variation of elastic modulus from negative to zero and then to positive witnesses the evolution process of stochastic P-bifurcation. From the vicinity of the common value to a wider range, the relaxation time induces the stochastic P-bifurcation in the two interval schemes.

Size structure of urban agglomerations in China:rationality evaluation,patterns, and implications

This paper establishes a diagnostic model for assessing the rationality of size structure of urban agglomerations(UAs) in China. The model is designed to determine from a three-dimensional index including size distribution index(SDI), size compactness index(SCI), and size efficiency index(SEI). The spatio-temporal pattern of size structure involving the studied 19 UAs and its implications are explored. The results indicate that size structure of China's UAs advanced from a low rationality development stage to a moderate rationality development stage in 1995-2015.Among them, the SDI and SEI were reasonably high, and the SCI was relatively low. Spatially, the high rationality UAs were distributed across eastern China, while the low rationality UAs were located in western China. UAs with positive size structure possessed typically a dual-or multicenter urban structure, while UAs with negative size structure usually presented as a single-center structure. The evolutionary trajectories of rationality of size structure of UAs can be summarized as four different stages. Our findings suggest that, in addition to consolidating the status of national-level UAs, the development of regional-level UAs should be promoted. Also, the fostering focus and direction should be oriented toward an UA with dual-or multicenter spatial structure.

Enhancing hydrogen electrocatalytic oxidation on Ni_(3)N/MoO_(2)in-plane heterostructures in alkaline solution

Nickel(Ni)-based materials act as one of the most promising candidates as platinum-group-metal-free(PGM-free)electrocatalysts for hydrogen oxidation reaction(HOR)in alkaline solution.Nevertheless,the electrocatalytic activity of pure Ni is significantly limited due to the sluggish kinetics under alkaline condition.To accelerate the kinetics,constructing heterostructures and nitride structures have been developed as two representative strategies.Here,we combined the two methods and presented a facile synthesis of the sheet-like Ni_(3)N/MoO_(2)in-plane heterostructures for enhanced HOR in alkaline electrolytes.Relative to Ni or Ni_(3)N,the Ni_(3)N/MoO_(2)in-plane heterostructures exhibited a significantly increased mass activity by 8.6-fold or 4.4-fold,respectively.Mechanistic studies revealed that the enhanced activity of Ni_(3)N/MoO_(2)could be attributed to the weakened hydrogen adsorption and strengthened hydroxyl adsorption.This work provides a facile approach to design high-efficiency catalysts for hydrogen-oxidation catalysis and beyond.

Engineering titanium oxide-based support for electrocatalysis

The corrosion and weaker interaction with metal catalysts of common carbon supports during electrocatalysis push the development of alternative supports materials. Titanium oxide-based materials have been widely explored as electrocatalysts supports in consideration of their chemical stability, strong interactions with metal catalyst and wider applications in electrocatalytic reactions as well as the improved electronic conductivity. This review summarizes recent research advances in engineering titanium oxide-based supports for the catalysts in electrocatalysis field to provide guidance for designing high performance non-carbon supported electrocatalysts. Typically, the titanium oxide-based supports are classified into shaped TiO_(2), doped TiO_(2), titanium suboxide and TiO_(2)-carbon composites according to the modification methods and corresponding preparation methods. Then the engineering strategies and electrocatalytic applications are discussed in detail. Finally, the challenges, future research directions and perspectives of titanium oxide-based supports for electrocatalysis are presented for practical applications.

Insight into the hydrogen oxidation electrocatalytic performance enhancement on Ni via oxophilic regulation of MoO_(2)

Exploring platinum-group-metal(PGM)free electrocatalysts for hydrogen oxidation reaction(HOR)in alkaline media is essential to the progress of anion exchange membrane fuel cells(AEMFCs).In this work,a Ni/MoO_(2) heterostructure catalyst with comparable HOR activity in alkaline electrolyte with PGM catalyst was prepared by a simple hydrothermal-reduction method.Remarkably,the Ni/MoO_(2) presents a mass kinetic current density of 38.5 mA mgNi^(-1) at the overpotential of 50 mV,which is higher than that of the best PGM free HOR catalyst reported by far.Moreover,the HOR performance of Ni/MoO_(2) under 100 ppm CO shows negligible fading,together with the superior durability,render it significant potential for application in AEMFCs.A particular mechanistic study indicates that the excellent HOR performance is ascribed to the accelerated Volmer step by the incorporation of MoO_(2).The function of MoO_(2) was further confirmed by CO striping experiment on Pt/C-MoO_(2) that MoO_(2) can facilitated OH adsorption thus accelerate the HOR process.On account of the high performance and low cost,the Ni/MoO_(2) electrocatalyst encourages the establishment of high performance PGM free catalyst and shows significant potential for application in AEMFCs.

Surface reconstruction enabled o-PdTe@Pd core-shell electrocatalyst for efficient oxygen reduction reaction

Palladium-based alloy catalysts have been employed as one of the potential candidates for oxygen reduc-tion reaction(ORR),but the dissolution of transition metal hinders their application.Herein,structure or-dered PdTe intermetallic with Pd shell(o-PdTe@Pd)are synthesized via an electrochemical etching driven surface reconstruction strategy.The surface reconstruction could tune the electronic structure,weaken the adsorption energy of reaction intermediates on o-PdTe@Pd,resulting in enhanced electrocatalytic ac-tivity for ORR.The mass activity of o-PdTe@Pd is about 3.3 and 2.7 times higher than that of Pd/C in acid and alkaline,respectively.Besides,the half-potentials for ORR decay only about 44 mV and 12 mV after 30 k cycles accelerated durability test in acid and alkaline media,respectively.The enhanced dura-bility originates from the resistance of Te atoms dissolve in the ordered PdTe intermetallic core and the core-shell structure.When assembled in a Zn-air battery,o-PdTe@Pd electrode delivers a higher specific capacity(794 mAh/g)and better cycling stability than Pt/C.

Manipulating fast Li_(2)S redox via carbon confinement and oxygen defect engineering of In_(2)O_(3)for lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries have been considered as promising energy storage systems due to the merits of high energy density and low cost.However,the lithium polysulfides(LiPSs)diffusion and sluggish redox kinetics hamper the battery performance.In this work,low-bandgap indium oxide(In_(2)O_(3))with dense oxygen vacancies(In_(2)O_(3−x),0<x<3)confined in nitrogen-doped carbon column(NC)is developed as a desirable LiPSs immobilizer and promoter to address these intractable problems.The NC confined In_(2)O_(3−x)with rich O vacancies(In_(2)O_(3−x)@NC)lowers the bandgap of 1.78 eV,strengthens the chemical adsorbability to LiPSs,and catalyzes the bidirectional Li_(2)S redox.Attributed to the structural and chemical cooperativities,the obtained sulfur electrodes exhibit a stable cycling over 550 cycles at 1.0 C and splendid rate capability up to 4.0 C.More significantly,when the sulfur-loading reaches as high as 5.5 mg·cm^(−2),the cathodes achieve an areal capacity of 5.12 mAh·cm^(−2)at 0.1 C.The strategy of NC confined catalyst with rich defects engineering demonstrates great promise in the development of practical Li-S batteries.

Recent progress in heterostructured materials for room-temperature sodium-sulfur batteries

Room-temperature sodium-sulfur(RT Na-S)batteries are a promising next-generation energy storage device due to their low cost,high energy density(1274 Wh kg^(-1)),and environmental friendliness.However,RT Na-S batteries face a series of vital challenges from sulfur cathode and sodium anode:(i)sluggish reaction kinetics of S and Na_(2)S/Na_(2)S_(2);(ii)severe shuttle effect from the dissolved intermediate sodium polysulfides(NaPSs);(iii)huge volume expansion induced by the change from S to Na_(2)S;(iv)continuous growth of sodium metal dendrites,leading to short-circuiting of the battery;(v)huge volume expansion/contraction of sodium anode upon sodium plating/stripping,causing uncontrollable solid-state electrolyte interphase growth and“dead sodium”formation.Various strategies have been proposed to address these issues,including physical/chemical adsorption of NaPSs,catalysts to facilitate the rapid conversion of NaPSs,high-conductive materials to promote ion/electron transfer,good sodiophilic Na anode hetero-interface homogenized Na ions flux and three-dimensional porous anode host to buffer the volume expansion of sodium.Heterostructure materials can combine these merits into one material to realize multifunctionality.Herein,the recent development of heterostructure as the host for sulfur cathode and Na anode has been reviewed.First of all,the electrochemical mechanisms of sulfur cathode/sodium anode and principles of heterostructures reinforced Na-S batteries are described.Then,the application of heterostructures in Na-S batteries is comprehensively examined.Finally,the current primary avenues of employing heterostructures in Na-S batteries are summarized.Opinions and prospects are put forward regarding the existing problems in current research,aiming to inspire the design of advanced and improved next-generation Na-S batteries.

Capture-SELEX for a short aptamer for label-free detection of salicylic acid

Salicylic acid(SA)is a hydrolysis product and an active form of aspirin,and SA is found in a range of fruits and other food products.For food and drug and analysis there is a strong desire to detect SA.Since SA is a very small molecule,aptamers have advantages over antibodies for its detection.In this work,we used the libraryimmobilization capture-SELEX method to isolate aptamers for SA.After 17 rounds of selection,two main families of aptamers were isolated.The SA1 aptamer from family 1 has a K_(d)of 5.8μM from a thioflavin T(ThT)fluorescence assay and 26.7μM from isothermal titration calorimetry.The binding of other sequences was weaker compared to SA1.Based on mutation studies,the two conserved regions of SA1 were connected by two stems.Using ThT as a stain,a label-free fluorescent sensor was tested for the detection of SA with a detection limit of 2.2μM.A few similar molecules were tested including aspirin,and only p-hydroxybenzoic acid showed a weak binding,indicating the high specificity of the SA1 aptamer.Finally,the SA1 aptamer was also tested in tomato juice and a similar binding performance was achieved.