Shape-Controlled Synthesis of Platinum-Based Nanocrystals and Their Electrocatalytic Applications in Fuel Cells

To achieve environmentally benign energy conversion with the carbon neutrality target via electrochemical reactions, the innovation of electrocatalysts plays a vital role in the enablement of renewable resources. Nowadays, Pt-based nanocrystals(NCs) have been identified as one class of the most promising candidates to efficiently catalyze both the half-reactions in hydrogen-and hydrocarbonbased fuel cells. Here, we thoroughly discuss the key achievement in developing shape-controlled Pt and Pt-based NCs, and their electrochemical applications in fuel cells. We begin with a mechanistic discussion on how the morphology can be precisely controlled in a colloidal system, followed by highlighting the advanced development of shape-controlled Pt, Pt-alloy, Pt-based core@shell NCs, Pt-based nanocages, and Pt-based intermetallic compounds. We then select some case studies on models of typical reactions(oxygen reduction reaction at the cathode and small molecular oxidation reaction at the anode) that are enhanced by the shape-controlled Pt-based nanocatalysts. Finally, we provide an outlook on the potential challenges of shape-controlled nanocatalysts and envision their perspective with suggestions.

Shape-controlled synthesis of novel precursor for fibrous Ni-Co alloy powders

A novel precursor of nickel-cobalt alloy powders with an appropriate Ni to Co molar ratio was prepared under selectively synthetic conditions. The composition and morphology of the precursor were characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, Fourier transform infrared spectrometry （FT-IR） and energy dispersive spectrometry （EDS）. The effects of pH value, reaction temperature, metal ion concentrations and surfactant on the morphology and the dispersion of precursor were investigated. The results show that the morphology of precursor depends on ammonia content in the precursor. A fibriform precursor is a complicated ammonia-containing nickel-cobalt oxalate. The uniform shape-controlled fibrous precursor is obtained under the following optimum conditions： ammonia as complex agent as well as pH adjustor, oxalate as coprecipitator, 50-65 °C of reaction temperature, 0.5-0.8 mol/L of total concentration of Ni2＋ and Co2＋, PVP as dispersant, and pH 8.0-8.4.

Shape-Controlled Synthesis of Palladium Nanoparticles and Their SPR/SERS Properties

Morphological evolution of Pd nanoparticles was studied in a solution-phase synthesis using cetyltrimethylammonium bromide （CTAB） and CTAB/sodium citrate mixture as capping agents, respectively. The morphological diversity of Pd nanoparticles is the combined effect of different Pd twinned seeds formed in the nucleation stage and selectively enlarging one set of crystallographic facets in the growth stage, both of which can be affected by the concentrations of CTAB. Through changing the concentrations of CTAB and sodium ascorbate, Pd nanoparticles with different shapes were obtained. When citrate ions were introduced to manipulate the nucleation and growth process, star-shaped icosahedra and nanorods with pentagram cross-sections were obtained. Pd nanoparticles with different shapes have quite different surface plasmon resonance and surface-enhanced Raman scattering properties.

A Convenient Method for Preparing Shape-controlled ZnO Nanocrystals in a Polyol/Water Mixture System without Surfactants

A facile solution-phase route for the synthesis of shape-controlled ZnO nanocrystals in a polyol/water mixture system was developed. The obtained nanocrystals were characterized by X-ray diffraction, transmission electron microscopy and UV-visible absorption spectroscopy. The results indicate that modulating the adding ways of water has a significant effect on the shape of the obtained nanocrystals. The addition of small quantity of water can increase the growth rate of crystals and leads to the formation of different shapes. The resulting shapes of the novel structures are diverse, including spheres, cones, and teardrops, all of which are obtained without any additional surfactants. These studies concerning the shape evolution of nanocrystals should be valuable for further design and for greater understanding of advanced nanoscale building-block architectures.

Shape-controlled Synthesis of Porous SnO_2 Nanostructures via Morphologically Conserved Transformation from SnC_2O_4 Precursor Approach

Porous SnO_2 nanostructures with controlled shapes were synthesized by a facile morphologically conserved transformation from Sn C_2O_4 precursor approach. Well-defined Sn C_2O_4 nanostructures can be obtained through a solution-based precipitation process at ambient conditions without any surfactant. The formation mechanism of such microstructures was tentatively proposed on the basis of intrinsic crystal structure and the reaction conditions. We found that the morphologies of precursor were well maintained while numerous pores were formed during the annealing process. The combined techniques of X-ray diffraction, nitrogen absorption–desorption, field emission scanning electron microscopy, and(high-resolution) transmission electron microscopy were used to characterize the as-prepared SnO_2 products. Moreover, cyclic voltammetry(CV) study shows that the shape of CV presents a current response like roughly rectangular mirror images with respect to the zero-current line without obvious redox peaks, which indicating an ideal capacitive behavior of the SnO_2 electrodes. The photoluminescence(PL) spectrum study suggests that the as-obtained porous SnO_2 nanostructures might have a large number of defects, vacancies of oxygen, and local lattice disorder at the interface, interior and exterior surfaces.

Shape-controlled synthesis of nanocubic Co_3O_4 by hydrothermal oxidation method

The nanocubic Co3O4 was synthesized by hydrothermal oxidation method. The effects of cobalt salt, precipitating agent, surfactant, solvent, pH value of the suspension and the amount of oxidant H2O2 on the morphology and structure of Co3O4 were investigated. The Co3O4 powders were characterized by transmission electron microscope and X-ray diffraction. The results show that the morphology of Co3O4 is closely dependant on the anion in cobalt salts, but it is not so sensitive to the precipitating agents and solvents. The amount of H2O2 is the key factor to obtain Co3O4 with spinel crystal structure. The optimum synthetic conditions of uniform shape-controlled Co3O4 nanocubes are as follows: Co(CH3COO)2·4H2O as cobalt salt, KOH as precipitating agent, polyethylene glycol with relative molecular mass of about 20 000 as surfactant, water-n-butanol as solvent system, pH value of 8-9, the molar ratio of H2O2 to Co2+ above 2.5∶1.0, hydrothermal temperature of 160 ℃ and hydrothermal holding time of 10 h. The tap density and apparent density of nanocubic Co3O4 obtained with the average particle size of 20 nm are 1.01 g/cm3 and 0.70 g/cm3, respectively.

开展城市设计工作,加强城市风貌管控

在我国城市高质量发展的背景下,中央对城市风貌及城市设计持续关注,城市风貌的塑造和管控成为重要议题。文章在对风貌工作的趋势要求进行解读的基础上,探讨了以山水格局、历史文脉、公共空间、建筑表现共同构成风貌感知要素的问题,通过景观可视、特色可辨、文脉可延、路径可游、建筑可读五个方面的途径来感知城市风貌。在把握城市风貌塑造和生成的特性及其规律的基础上,文章形成了“明确城市风貌定位–强化分区特色主题–细化引导风貌要素”的城市风貌塑造和管控方法,并提出了面向城市风貌塑造和管控,发挥城市设计优势,开展城市设计工作的建议。

基于时间动态规划的机身冗余控制对接算法

为了提高中机身的对接精度,保证对接效率,减小支撑底板受力变形,提出了一种基于调姿时间动态规划的机身冗余控制对接算法。根据机身初始位姿以及机身对接精度要求计算机身目标位姿,以姿态调整量和调姿速度为约束条件计算调姿时间,规划调姿轨迹。通过调姿轨迹计算定位器各轴驱动量,控制电机联动实现中机身调姿对接。仿真实验结果表明,经过基于调姿时间动态规划的冗余控制对接,飞机机身调姿定位过程中支撑底板无受力变形,减小调姿时间的同时对接精度相对较高,满足机身对接同轴度要求。

厚板轧制过程轧件翘扣头控制的有限元研究

利用ABAQUS有限元软件,模拟了厚板的轧制过程,计算了一系列可调控的工艺参数对轧件翘扣头的影响。可调控的工艺参数主要包括轧制中心线位置H i、上下轧辊的辊速差S k i和轧件上下表面温度差ΔT。计算结果表明,通过调整H_(i)、S_(ki)和ΔT,可以分别在2 m长度轧件上获得-17.5 mm、-181.0 mm和-200.0 mm的翘扣头控制量。进一步的分析表明,调节上下辊的辊速差、轧件上下表面温度差可较为有效地控制轧件翘扣头,且上下表面温度差对轧件翘扣头的控制能力更强。

基础隔震-外挂墙板减震钢筋混凝土框架振动台试验研究

该文提出一种新型的基础隔震-外挂墙板减震混合控制结构(简称“隔震-减震结构”)。该结构采用铅芯橡胶隔震支座作为基础隔震装置,上部结构则采用外挂墙板与U型金属消能器联合构成减震系统。通过减震与隔震混合控制,实现主体结构和围护墙体在罕遇地震下不发生损伤,可用于对韧性性能要求较高的生命线工程中。为对比研究隔震-减震结构与传统隔震结构的抗震性能,设计制作了一个在两方向上完全一致的1/2缩尺基础隔震钢筋混凝土框架结构,并在Y方向附加外挂墙板和U型金属消能器,形成隔震-减震结构,X方向不含外挂墙板,为隔震结构。分别在两个方向输入单向地震动进行振动台试验,试验结果表明:相比隔震结构,隔震-减震结构能进一步降低结构在设防和罕遇地震下的位移响应;隔震-减震结构在罕遇地震下最大层间位移角小于或接近钢筋混凝土框架结构弹性层间位移角限值,主体结构保持弹性,外挂墙板未出现损伤,可以实现预期的性能目标。

基于Arduino的SMA丝材智能修复损伤钢筋混凝土梁试验研究

为修复钢筋混凝土梁在使用阶段中由于材料老化、裂缝开展等原因造成的损伤,提出一种基于Arduino智能平台和形状记忆合金(Shape Memory Alloy,SMA,具有形状记忆效应和超弹性特性)的智能修复控制系统,根据挠度及裂缝控制原理,设计智能修复控制装置。该装置由输入模块、处理模块和输出模块组成,当检测到钢筋应变超过限值时,输出模块升高SMA丝材温度对梁体进行修复。为验证该智能修复装置的修复性能,设计对比梁A(无修复装置)与试验梁B(加装智能修复控制装置),在加载过程中对试验梁B进行3次修复,对2根梁的跨中挠度、钢筋应变及裂缝宽度等进行对比分析。结果表明:破坏时试验梁B的跨中挠度、裂缝宽度均小于对比梁A,并且在3次修复中试验梁B的跨中挠度、裂缝宽度和钢筋应变最大回复率分别为31.0%、47.0%和71.5%。说明该智能修复控制装置可以监测试验梁受损情况并激发SMA材料对试验梁实施修复,实现钢筋混凝土梁的智能修复。

冷连轧弯辊力精度改进PSO-SVM预测及补偿分析

为了进一步控制冷连轧弯辊力精度,构建改进PSO-SVM预测模型。利用包含压缩因子的粒子群算法完成支持向量机参数的更高效寻优处理,对回归轧制参数实施反归一化获得弯辊力模型。根据现场实际轧制结果完成预测模型的验证过程。研究结果表明:采用改进PSO-SVM模型获得的预测性能指标在上述优化方法中达到了最低,改进PSO-SVM模型具备最优预测效果。设置可靠补偿后大幅降低了AFC系统工作量,促进了带钢板形效率的显著提升。弯辊力补偿值形成了与弯辊力几乎相同的变化规律,具备优异预测性能。

形状记忆合金驱动的人工逼尿肌系统

针对神经源性、肌源性膀胱缺乏有效治疗手段的现状,从工程学角度提出了一种新的解决方案——人工逼尿肌系统。基于形状记忆合金(SMA)弹簧的形状记忆效应,设计了由无线能量传输模块、控制模块、反馈模块和执行模块组成的系统结构,旨在实现符合人体尿动力学规律的辅助排尿。文中首先建立了人体膀胱的有限元模型,仿真分析了人体膀胱的储尿和辅助排尿过程,在仿真结果的基础上结合SMA弹簧的数学模型,对SMA弹簧致动器的结构参数进行了优化设计;其次,结合实验数据推导了SMA弹簧温度-自由高度方程;然后,结合热力学公式和弹簧数学模型推导了系统控制方程,并在此基础上提出了系统开环控制策略;最后,基于系统的反馈模块,设计了比例积分微分(PID)闭环控制策略,并搭建模拟实验平台研究了系统的尿流率特性。结果表明:系统原理可行,辅助排尿过程连续可控,在应对不同尿液容量时两种控制策略均能实现符合人体尿动力学规律的辅助排尿。文中结果可为设计适用于临床的人工逼尿肌系统提供指导,也可为其他以SMA弹簧作为致动器的植入装置的设计提供借鉴和参考。

售货机升降系统S型速度控制策略

在传统三闭环控制方式下,售货机升降接货系统易因启停过程中加速度突变产生冲击,导致系统运行不平稳。针对这一问题,文中对传统升降系统加减速控制策略进行改进,加入前馈和微分负反馈,提出一种S型速度曲线控制算法。根据路径规划判别条件将S型速度曲线分为七段式、六段式和四段式3种,并给出各路径约束条件下的参数求解方法和具体执行流程。将该算法运用到升降控制系统中进行仿真和实际工况测试,实验结果表明,与传统三闭环控制相比,文中所提控制策略可以提高售货机升降系统运行的平稳性,减小冲击,使速度曲线更加柔和,并能够保持较好的跟踪性能。

高速飞行器气动控制耦合优化设计方法研究

针对传统串行设计过程由于空气动力学和控制系统数学模型复杂、无法综合考虑气动和控制的多目标优化的问题,提出了一种面向高速飞行器气动控制耦合优化设计方法。基于气动单学科代理优化(SBO)算法,将飞行器主动控制技术(ACT)的思想与多学科优化方法(MDO)相结合,构建了高速飞行器气动控制耦合多目标优化流程架构。在2马赫来流条件下,对带有控制舵的双锥体外形开展了气动耦合优化设计研究,以提升飞行器的气动性能和控制能力为优化目标。结果表明:经过气动控制耦合优化后的最优模型在超声速环境下,升力系数和升阻比分别提升了0.401%、2.999%,同时超调量与控制增益分别降低了2.769%、0.655%,气动性能和控制能力得到提升,验证了耦合策略的可行性;气动控制耦合优化的最优模型不仅使飞行器在超声速工作环境下性能更卓越,还有助于降低后续控制系统的设计难度,提高飞行器设计效率。所提气动控制耦合优化设计方法为高速飞行器的先进设计提供了必要的技术支撑。

分步液相还原法制备六方片状纳米银粉工艺研究

为探究分步液相还原法制备六方片状纳米银粉工艺条件对纳米银粉形貌及粒径的影响,以硝酸银为银源,过氧化氢为氧化刻蚀剂,硼氢化钠、抗坏血酸为还原剂,柠檬酸钠为形貌诱导剂,通过分步液相还原法制备出了六方片状纳米银粉。考察了制备工艺中晶种阶段过氧化氢用量、硼氢化钠用量、生长阶段柠檬酸钠用量、反应溶液pH值等工艺条件对纳米银粉形貌及粒径的影响规律,并分析了其影响机理。结果表明,当晶种阶段过氧化氢与硝酸银摩尔比为50∶1、硼氢化钠与硝酸银摩尔比为2∶1、生长阶段柠檬酸钠与硝酸银摩尔比为2∶1,反应溶液pH=8时,可制备出粒度分布均匀的六方片状纳米银粉,其六边形平均边长为40~60nm。晶种阶段过氧化氢用量是影响纳米银粉形貌的关键因素,随过氧化氢用量增大,纳米银粉形貌发生由类球状到片状的转化,过氧化氢过量可使片状纳米银粉边缘发生刻蚀作用;生长阶段反应溶液酸碱度是影响纳米银粉粒径的关键因素,随反应溶液pH值增大,纳米银粉平均粒径逐渐减小;柠檬酸钠可在纳米银粉表面发生选择性吸附,诱导纳米银粉发生各向异性生长,生成片状结构。

基于实测数据的飞机复合材料构件外形调控

在飞机复合材料构件装配中,目前常通过卡板等刚性约束方法消除其成型误差,这种调控方法可能会造成复合材料损伤。本文通过数字化测量获得复合材料构件实物外形数据,并重构其外形模型,设计了具有柔性的多点施力压头对构件进行外形调控。提出了将有限元计算与遗传算法相结合的求解方案,目标是在保证复合材料构件不发生损伤的前提下,使其实际外形尽量贴合理论外形。通过某型飞机雷达罩复合材料罩体实例验证此方法,发现按照利用约束卡板的原方案对罩体进行外形约束,其实际外形与理论外形在给定位置处精确度仅有66.7%,而通过本方法利用多点施力压头对罩体进行外形调控,其实际外形与理论外形在给定位置处精确度达到91.7%,相比原方案提高了25%。

高温合金环件形性协同锻造工艺参数群智能寻优方法与应用研究

准确快速地选取锻造工艺参数的最优组合方法,对实现难变形材料高温合金环类锻件的形性协同控制具有重要的意义。基于传统锻造工艺参数设计依赖设计人员经验、目标函数选择困难和寻优过程耗时等特点,提出了一种基于群智能寻优的工艺参数优化组合设计方法,实现了难变形高温合金环类锻件形性质量提升。论文以高温合金环形件模锻成形工艺参数最优组合为研究对象,以实现环锻件形性协同控制为目标,设计了考虑环锻件平均等效应变、等效应变标准差以及材料利用率的多目标参数模型;通过对各目标参数进行加权处理,获得了环锻件的综合目标模型;根据中心复合试验法及有限元模拟结果,确定了各目标参数与工艺参数之间的回归关系;利用麻雀搜索算法对综合目标模型进行智能寻优,获得了环锻件锻造工艺参数组合。生产试制结果表明:采用基于群智能寻优麻雀搜索算法获得的工艺参数组合,锻造后环锻件本体晶粒度达到9~10级,晶粒度差值小于1级,有效提高了环形锻件的变形均匀性,实现了高温合金环类锻件形状和性能的形性协同。

基于非线性修饰和零阶保持器的船舶航向保持控制

[目的]为了解决船舶在海上航行时控制器舵角输出大、打舵频率高、控制速度较慢以及控制精度较低的问题,利用三阶闭环增益成形算法设计鲁棒控制器。[方法]首先,利用三阶闭环增益成形算法设计出线性鲁棒控制器,然后,在控制策略中加入双曲正切非线性修饰以及零阶保持器,在不同海况下对该控制器的性能进行仿真实验。[结果]仿真结果表明,相比于基于非线性修饰的传统PID控制器,在一般海况下,所提控制器在延迟时间、控制精度以及能量输出上分别改进了36%,14%和32%;在恶劣海况下,分别改进了27%,7%和16%。此外,不同海况下该控制器的仿真结果都具有稳定的舵角输出,并可以较快地稳定在临界值附近,证明了其具有较好的鲁棒性。[结论]改进的控制器符合工程实践,对于智能船舶的控制具有较好的应用参考价值。

Shape-controlled synthesis of liquid metal nanodroplets for photothermal therapy

The capping agents for liquid metal (LM) nanodroplets in aqueous solutions are restricted to thiol-containing and positively-charged molecules or macromolecules.However,both thiolate-metal complex and electrostatic interaction are liable to detachment upon strong mechanical forces such as sonication,leading to limited stability and applications.To address this,we utilized ultrasmall water soluble melanin nanoparticles (MNPs) as the capping agent,which exhibited strong metal binding capability with the oxide layer of gallium based LMs and resulted in enhanced stability.Interestingly,shape-controlled synthesis of LM nanodroplets can be achieved by the incorporation of MNPs.Various EGaln nanostructures including nanorice,nanosphere and nanorod were obtained by simply tuning the feed ratio,sonication time,and suspension temperature.Among these shapes,EGaln nanorice has the best photothermal conversion efficiency,which could be leveraged for photothermal therapy.