Multiscale confinement nitridation in molybdenum carbide for efficient hydrogen production

The molybdenum carbide(Mo_(2)C)has been regarded as one of the most cost-efficient and stable electrocatalyst for the hydrogen evolution reaction(HER)by the virtue of its Pt-like electronic structures.However,the inherent limitation of high density of empty valence band significantly reduces its catalytic reactivity by reason of strong hydrogen desorption resistance.Herein,we propose a multiscale confinement synthesis method to design the nitrogen-rich Mo_(2)C for modulating the band structure via decomposing the pre-coordination bonded polymer in a pressure-tight tube sealing system.Pre-bonded c/N-Mo in the coordination precursor constructs a micro-confinement space,enabling the homogeneous nitrogenization in-situ happened during the formation of Mo_(2)C.Simultaneously,the evolved gases from the precursor decomposition in tube sealing system establish a macro-confinement environment,preventing the lattice N escape and further endowing a continuous nitridation.Combining the multiscale confinement effects,the nitrogen-rich Mo2C displays as high as 25%N-Mo concentration in carbide lattice,leading to a satisfactory band structure.Accordingly,the constructed nitrogen-rich Mo_(2)C reveals an adorable catalytic activity for HER in both alkaline and acid solution.It is anticipated that the multiscale confinement synthesis strategy presents guideline for the rational design of electrocatalysts and beyond.

Ethylene purification in a metal–organic framework over a wide temperature range via pore confinement

The separation of C2H4from C_(2)H_(6)/C_(2)H_(4)mixture is of great importance but difficult and energy intensive. Adsorptive separation provides an alternative approach to ameliorate this situation. Here, we report a microporous metal–organic framework(MOF) BUT-315-a as a C_(2)H_(6)-selective adsorbent for the separation of C2H6/C2H4gas mixture. BUT-315-a combines good IAST selectivity of 2.35 with high C_(2)H_(6)uptake of 97.5 cm^(3)g^(-1), giving superior high separation potential ΔQ(2226 mmol L^(-1)) for equimolar C_(2)H_(6)/C_(2)H_(4) at 298 K. Impressively, such excellent performance can be preserved at higher temperatures of 313 and 323 K to accommodate industrial conditions. Efficient dynamic separation performance of BUT-315-a has been demonstrated by column breakthrough experiments under varied temperatures and gas ratios. Theoretical calculations further reveal multiple synergistic interactions between C_(2)H_(6) and the framework. This work highlights a new benchmark material for C_(2)H_(6)/C_(2)H_(4)separation and provides guidance for designing adsorbent for separation applications.

Bacterial turbulence in gradient confinement

We investigate a novel form of non-uniform living turbulence at an extremely low Reynolds number using a bacterial suspension confined within a sessile droplet. This turbulence differs from homogeneous active turbulences in two or threedimensional geometries. The heterogeneity arises from a gradient of bacterial activity due to oxygen depletion along the droplet’s radial direction. Motile bacteria inject energy at individual scales, resulting in local anisotropic energy fluctuations that collectively give rise to isotropic turbulence. We find that the total kinetic energy and enstrophy decrease as distance from the drop contact line increases, due to the weakening of bacterial activity caused by oxygen depletion. While the balance between kinetic energy and enstrophy establishes a characteristic vortex scale depending on the contact angle of the sessile drop. The energy spectrum exhibits diverse scaling behaviors at large wavenumber, ranging from k-1/5to k-1,depending on the geometric confinement. Our findings demonstrate how spatial regulation of turbulence can be achieved by tuning the activity of driving units, offering insights into the dynamic behavior of living systems and the potential for controlling turbulence through gradient confinements.

Anion type-dependent confinement effect on glass transitions of solutions of LiTFSI and LiFSI

We present findings on the effect of nanometer-sized silica-based pores on the glass transition of aqueous solutions of lithium bis(trifluoromethane)sulfonimide(LiTFSI)and lithium difluorosulfimide(LiFSI),respectively.Our experimental results demonstrate a clear dependence of the confinement effect on the anion type,particularly for water-rich solutions,in which the precipitation of crystalized ice under cooling process induces the formation of freeze-concentrated phase confined between pore wall and core ice.As this liquid layer becomes thinner,the freeze-concentrated phase experiences glass transition at increasingly higher temperatures in solutions of LiTFSI.However,differently,for solutions of LiFSI and LiCl,this secondary confinement has a negligible effect on the glass transition of solutions confined wherein.These different behaviors emphasize the obvious difference in the dynamic properties’response of LiTFSI and LiFSI solutions to spatial confinement and particularly to the presence of the hydrophilic pore wall.

Experimental study of density gradient-driven micro-instabilities and the confinement degradation during H-mode in EAST

A broadband(BB)mode is observed by collective Thomson scattering diagnostics in repeatable shots of EAST and analyzed for the first time.This BB mode usually grows during L–H transitions,featuring a BB quasi-coherent mode with increasing frequency.During H-mode operations,it is characterized by steady-state BB in the high-frequency range(f~200–2000 k Hz),at the electron scale(k_(θ)ρ_(s)=1–2),mainly driven by the density gradient,and is sensitive to the value ofηein the region of interest(ρ=0.4–0.8),wherehe=(R/L_(Te))/(R/L_(ne))is the ratio of the normalized electron temperature gradient and density gradient,and the regionρ=0.4–0.8 usually has a relatively low collisionality(v_(eff)<5).The frequency of BB is found to be dependent on the electron temperature and density gradient,which is a typical feature of electron-driven turbulence.A negative correlation between the energy confinement and the intensity of the BB turbulence during H-mode has been found,which indicates a strong electron thermal transport induced by the BB turbulence.The BB significantly decreases the electron temperature and causes flatter electron temperature profiles in the region of interest(ρ=0.4–0.8),thus makingηedecrease and the BB destabilize further.These characteristics of BB are related to the theoretical density gradient-driven trapped electron mode.It should be noted that this mode is not observed by other diagnostics in EAST,and shows very different features to the coherent modes in the edge.

Single-Molecule Confinement Induced Intrinsic Multi-Electron Redox-Activity to Enhance Supercapacitor Performance

Aggregation of polyoxometalates(POM)is largely responsible for the reduced performance of POM-based energy-storage systems.To address this challenge,here,the precise confinement of single Keggin-type POM molecule in a porous carbon(PC)of unimodal super-micropore(micro-PC)is realized.Such precise single-molecule confinement enables sufficient activity center exposure and maximum electron-transfer from micro-PC to POM,which well stabilizes the electron-accepting molecules and thoroughly activates its inherent multi-electron redox-activity.In particular,the redox-activities and electron-accepting properties of the confined POM molecule are revealed to be super-micropore pore size-dependent by experiment and spectroscopy as well as theoretical calculation.Meanwhile,the molecularly dispersed POM molecules confined steadily in the“cage”of micro-PC exhibit unprecedented large-negative-potential stability and multiple-peak redox-activity at an ultra-low loading of~11.4 wt%.As a result,the fabricated solid-state supercapacitor achieves a remarkable areal capacitance,ultrahigh energy and power density of 443 mF cm^(-2),0.12 mWh cm^(-2)and 21.1 mW cm^(-2),respectively.This work establishes a novel strategy for the precise confinement of single POM molecule,providing a versatile approach to inducing the intrinsic activity of POMs for advanced energy-storage systems.

Implosion Plasma Driven Fusion Pellet of Inertial Confinement(A Short Memorandum)

The implosion plasma drive fusion pellet of inertial confinement is a concept related to nuclear fusion,a process in which atomic nuclei combine to form heavier nuclei,releasing a large amount of energy in the process.The implosion plasma drive fusion pellet is a potential fuel source for achieving controlled nuclear fusion.ICF(inertial confinement fusion)is a technique used to achieve fusion by compressing a small target containing fusion fuel to extremely high densities and temperatures using lasers or other methods.The implosion plasma drive fusion pellet concept involves using a small pellet of deuterium and tritium(two isotopes of hydrogen)as fusion fuel,and then rapidly heating and compressing it using a pulsed power system.The implosion process creates a high-pressure plasma that ignites the fusion reactions,releasing energy in the form of neutrons and charged particles.The resulting energy can be captured and used for power generation.This technology is still in the experimental stage,and significant research and development is required to make it commercially viable.However,it has the potential to provide a virtually limitless source of clean energy with no greenhouse gas emissions or long-term radioactive waste.Be that as it may,ICF has to get exact control of the implosion process,mitigate insecurities,and create modern materials and advances to resist the extraordinary conditions of the combined response.

RhCu催化剂中限域环境调控合成气转化生成CH_(x)反应性能

合成气制C2含氧化合物的选择性目前仍面临巨大挑战。本研究基于密度泛函理论计算方法,探究了4种RhCu限域催化剂中Rh活性位限域环境对合成气转化生成CH_(x)反应性能的影响,揭示了RhCu限域催化剂中限域效应调控催化性能的本质。结果表明,RhCu限域催化剂中Rh活性位限域环境能够调控合成气转化生成CH_(x)的活性和选择性。筛选获得RhGCN5.5催化剂具有最高的生成CH_(x)(x=1~3)单体活性,归因于适中的限域效应使得表层原子d带中心远离费米能级,导致CH2OH解离过渡态与RhCu表面之间呈现适当的电子转移,利于CH2OH解离,从而呈现良好的CH_(x)生成活性。本研究为通过调变单原子限域环境实现调控合成气转化生成C2含氧化合物反应的催化性能提供了理论依据,并为单原子限域金属催化剂设计提供了结构线索。

各向异性层状千枚岩渗透率及有效孔隙率试验研究

采用岩石全自动三轴伺服仪和气体渗透装置,对一种致密的各向异性层状千枚岩开展了气体渗透率及有效孔隙率试验,研究常规三轴压缩和围压循环加卸载2种应力路径下,气体渗透率、有效孔隙率随层理倾角及偏应力的演化规律。结果表明:围压相同时,岩样的初始气体渗透率k0随着层理倾角β的增大呈“W”型变化,在β=45°时取最大值;在围压循环加卸载过程中,气体渗透率先随围压的加载而减小,后随围压的卸载而增大,卸载时的气体渗透率小于加载时的渗透率;层状千枚岩有效孔隙率和气体渗透率呈指数关系;平行于层理方向的气体渗透率远大于垂直于层理方向的气体渗透率;岩样有效孔隙率和气体渗透率随偏应力变化经历初始压密阶段、线弹性阶段和塑性变形阶段,随着偏应力的增大,岩样有效孔隙率和气体渗透率先减小,接着保持稳定,最后快速增大,并在岩样应力-应变曲线斜率接近于0时达到最大值。

负载型MoS_(2)基加氢催化剂活性相的限域构建及其加氢脱硫活性

基于对负载型NiMo加氢脱硫催化剂活性相的结构设计,以具有内径10~30 nm直通孔道的天然埃洛石纳米管(HNT)为载体,利用其“孔道空间限域效应”作为MoS_(2)活性相结构的控制基础,以硫代钼酸铵和硝酸镍为金属前驱物,采用等体积浸渍法一次浸渍工艺,通过改变金属负载量、Ni/Mo(原子比)等工艺条件制备系列双金属NiMo/HNT催化剂。通过X射线衍射(XRD)、比表面积(BET)、高分辨透射电子显微镜(HRTEM-EDS mapping)、X射线光电子能谱仪(XPS)等手段对所得催化剂的结构进行表征,以二苯并噻吩(DBT)为模型化合物对催化剂的脱硫活性进行评价。结果表明:HNT载体的使用可有效控制MoS_(2)活性相尺寸,催化剂中的Mo、Ni金属组分几乎全部集中于载体的孔道内部并呈原生的亲密接触状态,同时Ni、Mo组分具有更高的硫化程度,协同效果更好;NiMo/HNT催化剂的加氢脱硫活性和加氢选择性均显著优于使用氧化铝载体的参比催化剂,其中DBT转化率最高增幅41.6%,反应速率R最大可以提升92%,加氢选择性最大可提升60%。

基于结构响应的舱室内爆TNT等效方法

[目的]旨在揭示爆轰产物后燃烧效应对封闭空间中爆炸载荷的影响规律。[方法]通过往封闭舱室中充入氮气来抑制爆轰产物燃烧,开展在空气和氮气两种不同气体环境下封闭舱室内TNT爆炸响应试验,记录温度、压力变化历程和靶板中心点残余挠度,建立基于无量纲载荷参数的靶板变形与炸药释放能量之间的关系,并提出考虑后燃烧效应的封闭空间TNT等效方法。[结果]结果发现,由于爆轰产物燃烧能量释放量不同,在氮气环境中,封闭空间内爆炸压力、温度和靶板动态响应明显低于空气环境。内爆载荷分析需计入TNT爆炸产物燃烧释放的能量及其增强效应。[结论]与现有基于准静态压力的TNT当量计算方法进行的比较表明,所提基于结构响应的舱室内爆TNT等效方法具有合理性和良好的适用性。

加卸载花岗岩强度与岩爆倾向性试验研究

为了进一步提高硬性花岗岩岩爆倾向性预测水平,系统开展了花岗岩巴西劈裂、单/三轴和不同卸围压速率应力路径下的岩石力学试验,详细分析了花岗岩强度和岩爆倾向性特征。研究结果表明:花岗岩在主应力σ_(3)–σ_(1)平面内,不同应力路径下的强度受围压和卸围压速率影响显著,呈带状分布;在τ_(oct)–(σ_(1)+σ_(3))/2平面内,不同加卸载应力路径下的强度都呈良好的线性特征。据此建立了花岗岩八面体强度计算通式,可统一表达不同加卸载应力路径;针对花岗岩硬岩的压密和屈服特性不明显,弹性特性显著的特征,提出了简化剩余弹性能指数岩爆分级法;并依据花岗岩试验岩样破坏形态和破坏声学特征,对已有花岗岩岩爆等级进行了细分。揭示了在相同初始围压下,卸围压速率越大,简化剩余弹性能指数越大,岩爆倾向性越强;相同卸围压速率下,初始围压越大,简化剩余弹性能指数也越大,岩爆倾向性也越强。研究成果可为更科学合理的评估花岗岩岩爆倾向性提供理论参考。

油雾爆燃机理实验平台的搭建与教学实验设计

为了探究受限空间内油雾爆燃事故机理及事故后果,设计了可视化的油雾爆燃机理测试实验平台。通过“实验平台功能需求分析-平台设计与开发-实验设计与实施-数据采集-结果分析”全过程,实现实验平台开发与各种船舶舱室、石油炼化生产过程及其他工业生产中油雾爆燃事故模拟实验。通过爆燃火焰传播规律、舱室内温度场、压力场的测试与分析,揭示了油雾爆燃发展规律。爆燃峰值压力可达0.9 MPa。爆燃温度较高,舱内峰值温度达到988℃,油雾爆燃破坏性较强。该实验增强了教学过程的直观性、交互性和多感知性,提高了学生的安全意识和解决复杂工程问题的探究能力,培养了学生的实践创新能力,提升了实践教学的质量。

小尺度靶丸冲击波调控的冲击波测量技术优化及应用

激光聚变研究中,冲击波调控技术是实现靶丸压缩过程的熵增调谐,保证高性能内爆的关键实验技术.本文在十万焦耳激光装置上首次实现了0.375 mm半径小尺度内爆靶丸下双台阶辐射驱动的高精度冲击波调控实验测量.针对小靶丸下任意反射面速度干涉仪(VISAR)诊断有效反射区域不足的问题,通过建立的球形反射面VISAR图像光强的理论计算方法,提出了利用锁孔(keyhole)锥反射效应提升VISAR诊断空间区域的实验技术路线,使得小靶丸尺度下有效VISAR数据区域提升了近3倍.在实验中首次获得了整形内爆实验条件下低温液氘靶的冲击波测量实验数据,实现了高精度冲击波调控实验测量.实验发现,小时空尺度内爆设计条件下,由于反射冲击波的作用,激光参数的较小偏差都会对冲击波追赶后的传输行为产生显著影响,揭示了我国当前小靶丸尺度下高性能整形内爆物理过程中冲击波传输的多因素敏感性,以及冲击波调控实验对于内爆设计验证的重要性.本文提出的小靶丸冲击波调控实验技术,不仅为我国十万焦耳激光装置上整形脉冲下熵增调谐实验的开展提供了技术基础,也对基于球汇聚压缩的超高压物理研究具有重要意义.

基于光纤光源的积分球内氘氘冰层红外均化设计

惯性约束聚变实验要求低温靶的冰层均匀性小于1μm。针对高均匀全固态氘氘冰层均化时缺乏β衰变热的问题,提出了基于光纤光源照明的积分球红外光均化方案。采用光线追迹耦合温度场的仿真技术,数值研究了光源位置以及入射角度对低温靶温度场的影响规律。研究结果表明,当红外光源功率为2.25 mW,入射位置Z=-7.3 mm,水平旋转角度为157.5°,冰层平均体加热率为24000 W/m3时,能够使冰层内表面最大温差满足0.1 mK的要求,满足冰层均化所需的温度场要求。本研究为后续进行基于积分球系统的红外均化低温靶制备实验提供了理论指导。

高围压状态下堆石料湿化变形特性

堆石料是土石坝的主要填筑材料,其湿化变形特性对土石坝蓄水期变形有显著影响。对两河口水电站的2种筑坝堆石料,采用单线法分别开展围压为0.5、1.0、2.0、3.0 MPa的大型三轴湿化变形试验。结果表明:随着应力水平和围压增加,堆石料轴向湿化变形和体积湿化变形都显著增大,与中低围压下的湿化变形规律相近。高围压下的各向等压湿化变形,堆石料体积湿化应变与围压在双对数坐标中仍服从直线关系,轴向湿化应变与围压不再满足直线关系。高围压下的偏压湿化变形,堆石料体积湿化应变与轴向湿化应变之比一般在0~2范围内,与围压呈现近似水平发展趋势,随应力水平的增加而逐渐降低。采用六参数湿化模型,仍能准确表达轴向湿化变形、体积湿化变形随应力水平、围压的变形规律。

不同围压及加载速率下的塑性混凝土动力特性研究

为研究塑性混凝土在三向应力状态下的动力特性与破坏规律,设计符合工程实践的配合比方案,借助动三轴试验仪开展了其在不同围压和不同加载速率条件下的强度、应力及应变规律研究。最后依据试验成果建立了基于Bresler-Pister三参数的强度准则。结果表明:塑性混凝土抗压强度与加载速率呈近线性正相关,材料抗压强度小于5.0MPa时对低加载速率更敏感,抗压强度大于5.0MPa时对高加载速率更敏感;不同加载速率下材料应力-应变规律基本一致,当应变达到1.47%~1.90%后其应力出现峰值,随后大幅度降低;不同围压条件下塑性混凝土抗压强度随围压的增加同样呈线性增长趋势,随着围压的提高,塑性混凝土峰值应力维持时间越长,材料抗裂性能越好;基于Bresler-Pister的强度准则公式其计算剪应力与三轴实测误差在1.61%~4.35%之间,基本反映了材料的变形破坏规律。

高阶轨道角动量传输光纤设计及传输特性研究(内封底文章)

为解决一般轨道角动量传输光纤传输轨道角动量模式数量少、质量差的问题,提出了一种基于正六边形空气孔排列的新型光子晶体光纤结构。该光纤引入了空气填充率高的矩形空气孔以及采用高折射率材料填充环形传输区域,能够有效提高环形传输区域和包层间的折射率差,且正六边形排列空气孔有利于提高模间有效折射率差。经过结构优化得到最优光纤结构,有限元法的分析结果表明,最优结构下,该光纤在常用波段S+C+L+U波段上能够支持142种轨道角动量模式的传输,最高阶数达到36阶。且所提出光纤具有良好的传输特性,本征模式的最高限制性损耗为10−9 dB/m量级,与典型轨道角动量传输光子晶体光纤相比至少降低了一个数量级;最大有效模场面积能够达到206.18μm^(2),最小非线性系数低至0.397 W^(−1)∙km^(−1);色散平坦且最小色散变化低至1.4578 ps/(nm∙km);所有本征模式纯度均在93.4%~96.8%范围内。且该光纤具有较好的制备可行性,对制造精度要求不高。因此,该光纤在基于轨道角动量光纤的复用系统中具有广阔的应用前景,为提高通信容量提供了一种有效手段。

送进式焊剂片约束电弧超窄间隙焊接工艺参数匹配

为探究送进式焊剂片约束电弧超窄间隙焊接的工艺参数匹配,自主设计制作了一套送进式焊剂片约束电弧超窄间隙焊接装置,以提高焊接过程稳定性和自动化水平。利用瞬间中断电弧的方法保留了熄弧位置处焊缝形态和焊剂片末端熔化形貌,发现焊接电压和焊剂带送进速度都是通过改变焊剂片对电弧的作用长度来影响焊缝成形,焊剂片对电弧的作用长度可表现为焊剂片对电弧固壁约束面积。通过改变焊剂带送进速度和焊接电压进行了试验研究,结果表明,当焊剂片对电弧固壁约束面积适中时,电弧集中加热区域会下移至间隙底部和侧壁根部,获得根部熔合良好的焊缝;当焊剂片对电弧固壁约束面积较大时,电弧受约束程度过强,电弧加热区域集中在间隙底部,分布于侧壁根部电弧热量很少,焊道上部会有熔池堆积;当焊剂片对电弧固壁约束面积较小时,电弧受约束程度较弱,会沿侧壁攀升导致加热区域集中在两侧壁上,很难在坡口根部形成有效熔池,最终形成孔洞焊缝。确定了最佳的焊接电压范围为21.5~24.5 V,焊剂带送进速度2.1~2.6 mm/s,利用该参数进行超窄间隙单道多层焊接可以获得成形良好的焊缝。

页岩凝析气受限空间相态及开发特征研究

涪页10井的钻探获取了东岳庙段典型陆相页岩相关特征参数,其页岩储层介孔和大孔发育,非均质性较强,主要孔隙分布在10nm左右。纳米孔中受限流体的临界参数偏移使得受限空间下凝析气的流体性质与常规室内实验测试结果存在差异。为更合理地开采页岩凝析气,结合室内相态实验、受限流体临界参数偏移计算和数值模拟,开展页岩凝析气相态特征分析和开采特征研究,明确凝析气的相态变化规律和开采特征。考虑临界参数偏移的凝析气相态特征计算表明:随着孔隙半径减小,体系组分的临界温度、临界压力降低,相图向左下收缩,露点压力降低,气相黏度降低,偏差因子增加,反凝析液饱和度逐渐降低。通过机理模型分析了临界参数偏移对衰竭开采效果的影响,结果表明:随着孔隙半径减小,天然气采收率基本不变,凝析油采收率逐渐增加,孔隙半径减小至10nm,凝析油采收率增加9.93%。研究结果对页岩凝析气藏开发具有指导意义。