Ribosome-inspired electrocatalysts inducing preferential nucleation and growth of three-dimensional lithium sulfide for high-performance lithium-sulfur batteries

Nucleation of lithium sulfide(Li_(2)S)induced by electrocatalysts plays a crucial role in mitigating the shut-tle effect.However,short-chain polysulfides on electrocatalysts surfaces tend to re-dissolve into elec-trolytes,delaying Li_(2)S supersaturation and its nucleation.In this study,we draw inspiration from the ribosome-driven protein synthesis process in cells to prepare ultrasmall nitrogen-doped MoS_(2) nanocrys-tals anchored on porous nitrogen-doped carbon networks(N-MoS_(2)-NC)electrocatalysts.Excitedly,the ex-situ SEM demonstrates that ribosome-inspired N-MoS_(2)-NC electrocatalysts induce early nucleation and rapid growth of three-dimensional Li_(2)s during discharge.Theoretical calculations reveal that the Li-s bond length in N-MoS_(2)-Li_(2)S(100)is shorter,and the corresponding interfacial formation energy is lower than in MoS_(2)-Li_(2)S(100).This accelerated conversion of lithium polysulfides to Li_(2)S can enhance the utilization of active substances and inhibit the shuttle effect.This study highlights the potential of ribosome-inspired N-MoS_(2)-NC in improving the electrochemical stability of Li-S batteries,providing valuable insights for future electrocatalyst design.

Nucleation of Supercooled Water by Neutrons: Latitude Dependence and Implications for Cloud Modelling

It has recently been shown that incident particles, neutrons, can initiate the freezing in a supercooled water volume. This new finding may have ramifications for the interpretation of both experimental data on the nucleation of laboratory samples of supercooled water and perhaps more importantly on the interpretation of ice nucleation involved in cloud physics. For example, if some fraction of the cloud nucleation previously attributed to dust, soot, or aerosols has been caused by cosmogenic neutrons, fresh consideration is required in the context of climate models. Moreover, as cosmogenic neutrons, most being muon-induced, have much greater flux at high latitudes, estimates of ice nucleates in these regions may be larger than required to accurately model cloud and condensation properties. This discrepancy has been pointed out in IPCC reports. Our paper discusses the connection between the new concept of neutrons nucleating supercooled water and the need for a new source of nucleation in high latitude clouds, ideally causing others to review current data, or to analyse future data with this idea in mind. .

Highly Reversible Zn Metal Anodes Enabled by Increased Nucleation Overpotential

Dendrite formation severely compromises further development of zinc ion batteries. Increasing the nucleation overpotential plays a crucial role in achieving uniform deposition of metal ions. However, this strategy has not yet attracted enough attention from researchers to our knowledge. Here, we propose that thermodynamic nucleation overpotential of Zn deposition can be boosted through complexing agent and select sodium L-tartrate(Na-L) as example. Theoretical and experimental characterization reveals L-tartrate anion can partially replace H_(2)O in the solvation sheath of Zn^(2+), increasing de-solvation energy. Concurrently, the Na^(+) could absorb on the surface of Zn anode preferentially to inhibit the deposition of Zn^(2+) aggregation. In consequence, the overpotential of Zn deposition could increase from 32.2 to 45.1 mV with the help of Na-L. The Zn-Zn cell could achieve a Zn utilization rate of 80% at areal capacity of 20 mAh cm^(-2). Zn-LiMn_(2)O_(4) full cell with Na-L additive delivers improved stability than that with blank electrolyte. This study also provides insight into the regulation of nucleation overpotential to achieve homogeneous Zn deposition.

Nucleation and growth control for iron-and phosphorus-rich phases from a modified steelmaking waste slag

Recovering the iron(Fe)and phosphorus(P)contained in steelmaking slags not only reduces the environmental burden caused by the accumulated slag,but also is the way to develop a circular economy and achieve sustainable development in the steel industry.We had pre-viously found the possibility of recovering Fe and P resources,i.e.,magnetite(Fe_(3)O_(4)) and calcium phosphate(Ca_(10)P_(6)O_(25)),contained in steel-making slags by adjusting oxygen partial pressure and adding modifier B_(2)O_(3).As a fundamental study for efficiently recovering Fe and P from steelmaking slag,in this study,the crystallization behavior of the CaO-SiO_(2)-FeO-P_(2)O_(5)-B_(2)O_(3) melt has been observed in situ,using a confocal scanning laser microscope(CLSM).The kinetics of nucleation and growth of Fe-and P-rich phases have been calculated using a classical crys-tallization kinetic theory.During cooling,a Fe_(3)O_(4) phase with faceted morphology was observed as the 1st precipitated phase in the isothermal interval of 1300-1150℃,while Ca_(10)P_(6)O_(25),with rod-shaped morphology,was found to be the 2nd phase to precipitate in the interval of 1150-1000℃.The crystallization abilities of Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases in the CaO-SiO_(2)-FeO-P_(2)O_(5)-B_(2)O_(3) melt were quantified with the in-dex of(T_(U)−T_(I))/T_(I)(where T_(I) represents the peak temperature of the nucleation rate and TU stands for that of growth rate),and the crystalliza-tion ability of Fe_(3)O_(4) was found to be larger than that of Ca_(10)P_(6)O_(25) phase.The range of crystallization temperature for Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases was optimized subsequently.The Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases are the potential sources for ferrous feedstock and phosphate fertilizer,respectively.

Inner-pore reduction nucleation of palladium nanoparticles in highly conductive wurster-type covalent organic frameworks for efficient oxygen reduction electrocatalysis

Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their poor conductivity represents the main obstruction to their practical application.Here,we reported a novel synthesis strategy for synergistically endowing a triphenylamine-based COFs with improved electrical conductivity and excellent catalytic activity for oxygen reduction,via the in-situ redox deposition and confined growth of palladium nanoparticles inside the porous structure of COFs using reductive triphenylamine frameworks as reducing agent;meanwhile,the triphenylamine unit was oxidized to radical cation structure and affords radical cation COFs with conductivity as high as3.2*10^(-1) S m^(-1).Such a uniform confine palladium nanoparticle on highly conductive COFs makes it an efficient electrocatalyst for four-electron oxygen reduction reaction(4e-ORR),showing excellent activities and fast kinetics with a remarkable half-wave potential(E_(1/2))of 0.865 V and an ultralow Tafel slope of 39.7 mV dec^(-1) in alkaline media even in the absence of extra commercial conductive fillers.The generality of this strategy was proved by preparing the different metal and metal alloy nanoparticles supported on COFs(Au@COF,Pt@COF,AuPd@COF,AgPd@COF,and PtPd@COF)using reductive triphenylamine frameworks as reducing agent.This work not only provides a facile strategy for the fabrication of highly conductive COF supported ORR electrocatalysts,but also sheds new light on the practical application of Zn-air battery.

Different roles of surfaces’ interaction on lattice mismatched/matched surfaces in facilitating ice nucleation

The freezing of water is one of the most common processes in nature and affects many aspects of human activity. Ice nucleation is a crucial part of the freezing process and usually occurs on material surfaces. There is still a lack of clear physical pictures about the central question how various features of material surfaces affect their capability in facilitating ice nucleation. Via molecular dynamics simulations, here we show that the detailed features of surfaces, such as atomic arrangements, lattice parameters, hydrophobicity, and function forms of surfaces’ interaction to water molecules, generally affect the ice nucleation through the average adsorption energy per unit-area surfaces to individual water molecules, when the lattice of surfaces mismatches that of ice. However, for the surfaces whose lattice matches ice, even the detailed function form of the surfaces’ interaction to water molecules can largely regulate the icing ability of these surfaces. This study provides new insights into understanding the diverse relationship between various microscopic features of different material surfaces and their nucleation efficacy.

Simultaneous refinement of α-Mg grains and β-Mg_(17)Al_(12) in Mg-Al based alloys via heterogeneous nucleation on Al_(8)Mn_(4)Sm

Due to the significant differences in the formation temperature and crystal structure between the primaryα-Mg and eutecticβ-Mg_(17)Al_(12),it is a great challenge to achieve simultaneous refinement of the primary and eutectic phases in Mg-Al based alloys via heterogeneous nucleation.Surprisingly,we found that theα-Mg andβ-Mg_(17)Al_(12) in the AZ80 alloy can be simultaneously refined after 0.2 wt.%Sm addition,with the grain size decreasing from∼217±15μm to∼170±10μm and theβ-Mg_(17)Al_(12) morphology changing from a typical continuous network to a nod-like or spherical structure.The simultaneous refinement mechanism is investigated through solidification simulation,transmission electron microscopy(TEM),and differential thermal analysis(DTA).In the AZ80-0.2Sm alloy,many Al8Mn4Sm particles can be observed near the center of theα-Mg grains or inside theβ-Mg_(17)Al_(12).Crystallographic calculations further reveal that the Al8Mn4Sm has good crystallographic matching with both theα-Mg andβ-Mg_(17)Al_(12),so it possesses the potency to serve as heterogeneous nucleation sites for both phases.The promoted heterogeneous nucleation on the Al8Mn4Sm decreases the undercooling required by the nucleation of the primary and eutectic phases,which enhances the heterogeneous nucleation rate,thus causing the simultaneous refinement of theα-Mg andβ-Mg_(17)Al_(12).The orientation relationships between the Al8Mn4Sm and Mg/Mg_(17)Al_(12) are identified,which are[1210]_(Mg)//[010]_(Al8Mn4Sm),(1010)_(Mg)//(301)_(Al8Mn4Sm) and[112]_(Mg_(17)Al_(12))//[010]_(Al8Mn4Sm),(110)_(Mg_(17)Al_(12))//(301)_(Al8Mn4Sm),respectively.Furthermore,the refinement of theβ-Mg_(17)Al_(12) accelerates its dissolution during the solution treatment,which is beneficial for cost saving in industrial applications.Other Al8Mn4RE compounds such as Al8Mn4Y might have the same positive effect on the simultaneous refinement due to the similar physicochemical properties of rare earth elements.This work not only proves the possibility of simultaneously refining the primary and eutectic phases in Mg-Al based alloys via heterogeneous nucleation,but also provides new insights into the development of refiners for cast Mg alloys.

Bubble nucleation in spherical liquid cavity wrapped by elastic medium

According to classical nucleation theory, gas nuclei can generate and grow into a cavitation bubble when the liquid pressure exceeds a threshold. However, classical nucleation theory does not include boundary effects. An enclosed spherical liquid cavity surrounded by elastic medium is introduced to model the nucleation process in tissue. Based on the equilibrium pressure relationship of a quasi-static process, the expressions of the threshold and the modified nucleation rate are derived by considering the tissue elasticity. It is shown that the constraint plays an important role in the nucleation process. There is a positive correlation between nucleation threshold pressure and constraint, which can be enhanced by an increasing tissue elasticity and reducing the size of the cavity. Meanwhile, temperature is found to be a key parameter of nucleation process, and cavitation is more likely to occur in confined liquids at temperature T > 100℃. In contrast, less influences are induced by these factors, such as bulk modulus, liquid cavity size, and acoustic frequency. Although these theoretical predictions of the thresholds have been demonstrated by many previous researches, much lower thresholds can be obtained in liquids containing dissolved gases, e.g., the nucleation threshold is about-21 MPa in a liquid of 0.8-nm gas nuclei at room temperature. Moreover, when there is a gas nucleus of 20 nm, the theoretical threshold pressure might be less than1 MPa.

聚丙烯/蒙脱土纳米复合材料的制备与力学性能预测

本文采用熔融挤出法制备了β成核聚丙烯/蒙脱土纳米复合材料,考察了蒙脱土、β成核剂及增容剂用量对复合材料缺口冲击强度和弯曲强度的影响,并用BP神经网络进行预测。结果表明,增加蒙脱土用量有助于复合材料强度的提高但对韧性不利;随β成核剂用量的增加,复合材料的缺口冲击强度略有增加,而弯曲强度存在最优值,即添加β成核剂0.1%时,弯曲强度达到最大值35.06MPa,较不添加时增加了13.68%;随增容剂用量的增加,复合材料的韧性显著增大而强度有所降低,添加30%增容剂,复合材料的缺口冲击强度较不添加时增加了约3倍,而弯曲强度仅降低了28.39%;BP神经网络预测结果表明,该模型能够比较精确的预测该复合材料的力学性能。该研究对于优化聚丙烯基纳米复合材料制备及改进力学性能预测具有借鉴意义。

不同预时效挤压态Mg−Gd−Y−Zn−Zr合金的再结晶行为和强化机制

通过控制预时效时间制备3种不同状态的试样,研究不同预时效状态对挤压态Mg−9.5Gd−4Y−2.2Zn−0.5Zr(质量分数,%)合金的动态再结晶行为(DRX)和性能的影响。结果表明,欠时效挤压(UAE)样品的细晶体积分数为17.4%,而峰时效挤压(PAE)和过时效挤压(OAE)样品的细晶体积分数分别达到89.7%和50.4%。在晶粒内部和晶界处分布的致密、细小的β颗粒相通过粒子激发形核机制显著提高了形核位点和位错密度。然而,致密针状γ'相抑制位错滑移,延迟DRX形核。PEA和OAE样品中细小晶粒的差异归因于原始颗粒相的数量和尺寸的不同,而其拉伸性能的差异归因于不同的显微组织。由于晶界强化和析出强化机制的贡献更大,PAE样品具有更优异的拉伸性能。

EICP与木质素联合改性粉土边坡抗雨蚀试验研究

通过设置6组试样,采用降雨试验,通过试样的表面侵蚀状况与冲蚀量、表面强度、碳酸钙含量的变化分析了改性后粉土边坡的抗雨蚀性能。试验结果表明:植物源酶诱导碳酸钙沉淀(EICP)与木质素联合改性试样并在表面喷洒EICP溶液后,试样表面完整度更好,表面强度及碳酸钙含量更高,质量损失更小,抗雨蚀能力明显提高,与其他试样的平均值相比,边坡土体侵蚀量降低了75.0%,表面强度提高了33.8%,碳酸钙含量提高了235.2%;坡面喷洒EICP溶液可形成硬壳层,有效避免坡面侵蚀;木质素可为碳酸钙提供成核位点,使分布散乱的碳酸钙附着在木质素上,添加木质素后试样碳酸钙含量提高,且表面强度随碳酸钙含量提高而增大。

纳米凹槽表面结冰的分子动力学模拟研究

采用分子动力学模拟方法建立了水在金表面结冰的模型,在疏水表面上引入亲水纳米凹槽结构,模拟研究了纳米凹槽表面上的冰成核过程,揭示了凹槽深宽比对冰成核的影响规律和机制.结果表明,在疏水表面引入亲水纳米凹槽结构并改变表面的凹槽宽度,可以调节疏水表面的结冰过程.当纳米凹槽与六边形冰结构相匹配时,凹槽内部更容易形成冰核,可以提高疏水表面的冰成核率的效果,其表面成核率接近与亲水表面成核率.当纳米凹槽结构与六边形冰结构不匹配时,凹槽内不易形成冰核,结冰过程受到抑制.为提高疏水表面成核率提供了新方法,为控制疏水表面冰成核位置和冰生长方向提供了新思路.

断层接触非均匀性对米尺度断层黏滑失稳成核过程的控制

非均匀性是野外断层的重要特征,我们利用预制的具备接触非均匀性的米尺度岩石断层开展黏滑实验,模拟野外地震失稳过程.通过观测预制岩石断层发生的多个黏滑事件的应变时空演化,并对比断层接触非均匀性测定结果发现:(1)断层的接触弱段是成核最先启动,即最早发生预滑的区域,随失稳临近,预滑区域扩展且滑动速率增加,与厘米尺度均匀断层相比,准静态过程的预滑扩展不明显,向准动态过程转变突然且迅速;(2)断层的接触强段在成核期间一直处于闭锁状态,应力升高,且随失稳临近增幅加强,强段的屈服是断层从缓慢破裂到快速破裂的转折点,接触强段的持续闭锁在以往的厘米尺度均匀断层黏滑实验中较为少见;(3)加载速率以及加载历史是影响米尺度断层成核持续时间的重要因素,随加载速率变慢,成核持续时间变长,随加载历史变长,断层趋于均匀化,成核持续时间变短.上述研究结果明确提供断层接触非均匀性控制成核过程的直接证据.这不仅有助于将实验结果向可操作的地震预测实践转化,也有助于促进(大陆浅源)地震前兆机理的探索及理解.

真空羽流中相变过程DSMC仿真方法研究

真空燃气羽流快速膨胀过程中,其中的H_(2)O和CO_(2)等组元容易发生凝结相变现象.为了研究真空羽流中水蒸气的相变产物冰晶对羽流红外信号、侵蚀等污染效应的影响,开展羽流中相变过程的数值模拟方法研究.基于稀薄两相羽流双向耦合DSMC方法,采用经典成核理论和液滴生长理论,建立了真空羽流的相变过程的数值仿真方法.对水蒸气在拉法尔喷管中自凝结试验的仿真.通过与试验结果的对比,对经典成核理论进行了修正,对成核率给出了10^(3)的修正因子,可以得到与试验符合的仿真结果,表明对成核理论修正后,可以应用到稀薄流动的数值模拟中.对某发动机真空羽流相变流场的仿真,在核心区得到与CFD相近的结果.仿真结果表明,在羽流流场中,由于相变,存在较多的冰晶颗粒,在计算条件下,羽流核心区冰晶数密度最大达到10^(15) m^(-3)的量级,冰晶直径在约10^(-8) m的量级.在真空环境下,随着羽流向倒流区无限制膨胀,倒流区流场内也会出现一定数量的冰晶颗粒,数密度从10^(7)~10^(10)m^(-3)的量级,直径在5.0×10^(-10)m的量级.颗粒在空间的数密度、尺寸等分布与气相分布存在差异,需要开展相关污染效应的影响研究.

利用废岩棉制备高性能泡沫玻璃陶瓷的实验研究

以工业垃圾废岩棉和废玻璃为原料,以CaCO_(3)为发泡剂制备出高强度泡沫玻璃陶瓷。研究了废岩棉和废玻璃的添加量及烧结温度对泡沫玻璃陶瓷材料性能的影响。结果表明:随着废岩棉添加量的增加和烧结温度的提高,熔体黏度会降低,不利于气泡结构的稳定;在废岩棉添加量为40%、750℃烧结温度下得到的样品容重为0.54 g/cm^(3)、孔隙率为62.5%、抗压强度为4.76 MPa;样品主晶相为亚硅酸钙和石英晶相,加入TiO_(2)作为晶核剂后主晶相改变为榍石;TiO_(2)掺量为10%时,在750℃烧结20 min更经济,所得样品容重为0.82 g/cm^(3)、孔隙率为50%、抗压强度为7.76 MPa。

无规共聚透明聚丙烯的研发

研究了不同成核剂种类和用量对无规共聚聚丙烯(PP)RP210M透明性的影响。通过优化复合助剂配方,成功工业化生产了无规共聚透明PP产品(PP-E800),综合性能好于对标产品。

微生物矿化反应原理、沉积与破坏机制及理论:研究进展与挑战

微生物矿化作为地质演变及碳氮循环不可或缺的一环,给岩土、水利及环境等领域带来了新的机遇和挑战,其衍生而来的以MICP为代表的微生物岩土技术已成为环境岩土工程最具革新性的技术领域之一。近20年来,微生物岩土技术从概念验证阶段到相关领域技术示范已取得了重要进展。为推进对该领域更加深入的基础认识与研究,本文系统回顾了MICP技术并针对以下3部分进行了重点阐述:脲酶菌成矿作用的生物化学原理、微生物加固土的沉积模式及加固体破坏机理、涉及生物-化学-水力-力学等多物理场耦合作用下的微生物矿化反应理论。此外,还总结了微生物岩土技术目前亟待解决的问题与挑战,对潜在的研究热点与应用前景进行了探讨和展望。

Sc和Si相互作用对铸造Al-Si-Sc合金组织和性能的影响

通常在铸造Al-Si合金加入Sc来改善合金的性能,但是Si和Sc的相互作用对合金组织和性能影响仍需要进一步深入研究。本文研究了不同含量的Si和Sc对合金组织和性能的影响,结果表明,Sc通过原位形成初生Al_(3)Sc作为α-Al异质形核质点从而细化α-Al晶粒;在凝固过程中,共晶反应生成了网格状AlSi_(2)Sc_(2)相,包晶反应形成了块状AlSi_(2)Sc_(2)相;两种AlSi_(2)Sc_(2)相都会消耗合金中Sc原子,从而降低了Al_(3)Sc的细化效果;Sc还变质共晶Si为更有序的纤维/片状结构,适当的Si与Sc的比可以避免AlSi_(2)Sc_(2)的形成;Al-6Si中Sc含量从0.3%增加至1%时,抗拉强度和屈服强度均上升,但由于AlSi_(2)Sc_(2)相的存在,其伸长率下降;当Sc含量为1%、Si含量从6%降至3%时,抗拉强度、屈服强度和伸长率分别上升2%、12%和21%,主要是凝固过程中析出了Al_(3)Sc而非AlSi_(2)Sc_(2)相。最后,还讨论了Si-Sc交互作用对组织演变的机制。

β成核聚丙烯/蒙脱土纳米复合材料的结构与力学性能

本文使用双螺杆挤出机制备了β成核聚丙烯(β-PP)/有机蒙脱土(OMMT)纳米复合材料。采用FTIR、XRD和SEM分析了复合材料的微观结构与形貌特征,考察了OMMT、β成核剂(β-NA)及增容剂用量对复合材料冲击强度和弯曲强度的影响,并对比研究了标准BP神经网络模型和LM-BP神经网络模型对力学性能的预测能力。结果表明,增容剂与OMMT表面形成了强相互作用,提高了复合体系的相容性,黏土片以插层结构分散在β-PP基体内。OMMT、β-NA及增容剂用量对复合材料的力学性能均产生了一定影响,其中添加30%增容剂时复合材料的冲击强度约为不添加时的4倍,而弯曲强度仅降低了28.39%。此外,与标准BP神经网络模型相比,LM-BP神经网络模型具有更快的收敛速度和更高的预测精度。该研究为优化PP基纳米复合材料的制备及力学性能预测提供了参考。

钢桥复杂构造疲劳裂纹跨尺度扩展与寿命预测

针对传统宏观唯像学方法无法描述钢桥疲劳损伤由微观到宏观的多尺度演化过程的问题,建立了可描述钢桥复杂构造疲劳裂纹跨尺度扩展与寿命预测方法.首先,结合微观晶体塑性本构模型,建立了以能量耗散理论为基础的微观短裂纹成核与扩展模型.同时,结合线弹性断裂力学,建立了宏观长裂纹扩展模型.在此基础上,以钢桥典型的纵肋与顶板焊接构造细节为研究对象,结合既有疲劳试验,模拟并验证了微观短裂纹的成核、扩展,以及宏观长裂纹扩展全过程.数值模拟结果与试验结果基本一致,表明所提出的疲劳裂纹跨尺度扩展与寿命预测方法对于钢桥复杂构造细节疲劳损伤演化与评估具有较好的适用性.