运用三维离散元技术模拟落锤撞击下奥克托今颗粒的点火燃烧过程

炸药颗粒的点火燃烧过程一直是人们关注的热点问题。近年来，三维离散元技术在中尺度观测颗粒材料的动力学过程中拥有显著优势。炸药燃烧属于颗粒材料的反应动力学，运用三维离散元技术(DM3)可以有效地观测炸药燃烧传播的过程。以奥克托今(HMX)颗粒为例，本文成功模拟并观测到了HMX颗粒的燃烧反应程度，确定了颗粒开始燃烧反应的时间，以及燃烧反应传播的时间。同时，结合落锤冲击颗粒的三维图像以及其表观压强和放热功率，得到了HMX颗粒燃烧反应、燃烧传播的整个反应动力学过程，包括颗粒在冲击加载下碎化塑性变形的过程，颗粒燃烧反应放热的过程，落锤回弹颗粒喷射的过程等。同时，进一步说明了尖顶颗粒更利于颗粒点火，平顶颗粒有抑制颗粒点火的能力。     

An improved evaluation of the neutron background in the PandaX-Ⅱ experiment

In dark matter direct detection experiments,neutron is a serious source of background,which can mimic the dark matter-nucleus scattering signals.In this paper,we present an improved evaluation of the neutron background in the PandaX-II dark matter experiment by a novel approach.Instead of fully relying on the Monte Carlo simulation,the overall neutron background is determined from the neutron-induced high energy signals in the data.In addition,the probability of producing a dark-matter-like background per neutron is evaluated with a complete Monte Carlo generator,where the correlated emission of neutron(s)andγ(s)in the(α,n)reactions and spontaneous fissions is taken into consideration.With this method,the neutron backgrounds in the Run 9(26-ton-day)and Run 10(28-ton-day)data sets of PandaX-II are estimated to be(0.66±0.24)and(0.47±0.25)events,respectively.     

Tribological behaviors of DLC films in sulfuric acid and sodium hydroxide solutions

Tribological behaviors of three typical kinds of diamond-like carbon (DLC) films (a-C, a-C:Cr, and a-C:H) in sulfuric acid and sodium hydroxide solutions were investigated. The a-C film showed the lowest stable coefficients of friction (COF) in both sulfuric acid and sodium hydroxide solutions but the worst wear resistance in sulfuric acid solution. The a-C:H film showed the highest COF in sulfuric acid solution and the best wear resistance in both sulfuric acid and sodium hydroxide solutions. The a-C:Cr film exhibited superior comprehensive tribological performance in sulfuric acid solution, while in sodium hydroxide solution, high COF and very poor wear resistance was observed. What is more, friction and wear mechanism was revealed by investigating the friction-induced material evolutions on the sliding surface.     

N-Doped Graphdiyne Coating for Dendrite-Free Lithium Metal Batteries

Nonuniform nucleation is one of the major reasons for the dendric growth of metallic lithium, which leads to intractable problems in the efficiency, reversibility, and safety in Li-based batteries. To improve the deposition of metallic Li on Cu substrates, herein, a freestanding current collector (NGDY@CuNW) is formed by coating pyridinic nitrogen-doped graphdiyne (NGDY) nanofilms on 3D Cu nanowires (CuNWs). Theoretical predictions reveal that the introduction of nitrogen atoms in the 2D GDY can enhance the binding energy between the Li atom and GDY, therefore improving the lithiophilicity on the surface for uniform lithium nucleation and deposition. Accordingly, the deposited metallic Li on the NGDY@CuNW electrode exhibits a dendrite-free morphology, resulting in significant improvements in terms of the reversibility with a high coulombic efficiency (CE) and a long lifespan at high current density. Our research provides an efficient method to control the surface property of Cu, which also will be instructive for other metal batteries.     

泡沫镍铁合金自支撑NiFeOOH纳米片的制备及析氧性能研究

电催化析氧反应(OER)是电解水制氢的重要半电池反应。然而,OER的缓慢动力学仍需研究高效的电催化剂。在非贵金属催化剂中,NiFe基材料是OER催化剂研究热点。本文通过食人鱼溶液简单一步浸渍刻蚀法将不同Fe含量的泡沫NiFe合金进行氧化,制备了表面具有纳米片形貌的NiFeOOH自支撑电催化剂,并深入研究其电催化析氧性能。通过SEM、XRD、XPS等对电催化剂的形貌结构及成分进行表征,证实了三维多孔基底上NiFeOOH纳米片结构的形成。由于高价镍、铁物种的存在以及二维纳米片结构的生成,NiFeOOH/NF的析氧性能大幅度提高,在10 mA?cm-2的电流密度下过电位仅155.68 mV,Tafel斜率为 88.2 mV?dec-1。这为研制高效、耐用的自支撑非贵金属电极提供了新思路。     

A Robust Metal-Organic Framework with Scalable Synthesis and Optimal Adsorption and Desorption for Energy-Efficient Ethylene Purification

Adsorptive separation is an energy-efficient alternative, but its advancement has been hindered by the challenge of industrially potential adsorbents development. Herein, a novel ultra-microporous metal-organic framework ZU-901 is designed that satisfies the basic criteria raised by ethylene/ethane (C₂H₄/C₂H₆) pressure swing adsorption (PSA). ZU-901 exhibits an “S” shaped C₂H₄ curve with high sorbent selection parameter (65) and could be mildly regenerated. Through green aqueous-phase synthesis, ZU-901 is easily scalable with 99 % yield, and it is stable in water, acid, basic solutions and cycling breakthrough experiments. Polymer-grade C₂H₄ (99.51 %) could be obtained via a simulating two-bed PSA process, and the corresponding energy consumption is only 1/10 of that of simulating cryogenic distillation. Our work has demonstrated the great potential of pore engineering in designing porous materials with desired adsorption and desorption behavior to implement an efficient PSA process.     

Tuning the CO2 Hydrogenation Selectivity of Rhodium Single-Atom Catalysts on Zirconium Dioxide with Alkali Ions

Tuning the coordination environments of metal single atoms (M₁) in single-atom catalysts has shown large impacts on catalytic activity and stability but often barely on selectivity in thermocatalysis. Here, we report that simultaneously regulating both Rh₁ atoms and ZrO₂ support with alkali ions (e.g., Na) enables efficient switching of the reaction products from nearly 100 % CH₄ to above 99 % CO in CO₂ hydrogenation in a wide temperature range (240–440 °C) along with a record high activity of 9.4 mol_CO g_Rh⁻¹ h⁻¹ at 300 °C and long-term stability. In situ spectroscopic characterization and theoretical calculations unveil that alkali ions on ZrO₂ change the surface intermediate from formate to carboxy species during CO₂ activation, thus leading to exclusive CO formation. Meanwhile, alkali ions also reinforce the electronic Rh₁-support interactions, endowing the Rh₁ atoms more electron deficient, which improves the stability against sintering and inhibits deep hydrogenation of CO to CH₄.     

Solar-Driven CO2 Conversion via Optimized Photothermal Catalysis in a Lotus Pod Structure

Photothermal CO₂ reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium-modified carbon-supported cobalt (K⁺−Co−C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus-pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K⁺−Co−C catalyst shows a record-high photothermal CO₂ hydrogenation rate of 758 mmol g_cat⁻¹ h⁻¹ (2871 mmol g_Co⁻¹ h⁻¹) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO₂ reduction reactions. We further demonstrate with this catalyst effective CO₂ conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.     

Promoter-Controlled Synthesis and Conformational Analysis of Cyclic Mannosides up to a 32-mer

Cyclodextrins are widely used as carriers of small molecules for drug delivery owing to their remarkable host properties and excellent biocompatibility. However, cyclic oligosaccharides with different sizes and shapes are limited. Cycloglycosylation of ultra-large bifunctional saccharide precursors is challenging due to the constrained conformational spaces. Herein we report a promoter-controlled cycloglycosylation approach for the synthesis of cyclic α-(1→6)-linked mannosides up to a 32-mer. Cycloglycosylation of the bifunctional thioglycosides and (Z)-ynenoates was found to be highly dependent on the promoters. In particular, a sufficient amount of a gold(I) complex played a key role in the proper preorganization of the ultra-large cyclic transition state, providing a cyclic 32-mer polymannoside, which represents the largest synthetic cyclic polysaccharide to date. NMR experiments and a computational study revealed that the cyclic 2-mer, 4-mer, 8-mer, 16-mer, and 32-mer mannosides adopted different conformational states and shapes.     

Photocatalytic Free Radical-Controlled Synthesis of High-Performance Single-Atom Catalysts

Single-atom catalysts (SACs) have emerged as crucial players in catalysis research, prompting extensive investigation and application. The precise control of metal atom nucleation and growth has garnered significant attention. In this study, we present a straightforward approach for preparing SACs utilizing a photocatalytic radical control strategy. Notably, we demonstrate for the first time that radicals generated during the photochemical process effectively hinder the aggregation of individual atoms. By leveraging the cooperative anchoring of nitrogen atoms and crystal lattice oxygen on the support, we successfully stabilize the single atom. Our Pd₁/TiO₂ catalysts exhibit remarkable catalytic activity and stability in the Suzuki–Miyaura cross-coupling reaction, which was 43 times higher than Pd/C. Furthermore, we successfully depose Pd atoms onto various substrates, including TiO₂, CeO₂, and WO₃. The photocatalytic radical control strategy can be extended to other single-atom catalysts, such as Ir, Pt, Rh, and Ru, underscoring its broad applicability.