去合金化制备纳米多孔铜及铜合金的最新研究进展

纳米多孔铜及铜合金能够通过去合金化法进行高效可控的制备,由于其展现出优异的物理和化学性能,并且价格低廉,有望取代纳米多孔贵金属(如多孔金等),在催化、生物传感器、能源等领域展现巨大的应用潜力。系统地总结了近5年来纳米多孔铜及铜合金在去合金化孔洞形成机理、制备工艺探索、性能表征及应用方面的一些最新研究进展。在此基础上提出纳米多孔铜及铜合金3个最有可能的研究方向。     

孔隙可调控多孔铜粉的气相去合金制备及性能研究

多孔铜粉具有独特的孔隙结构和大比表面积,是适合于催化生长和化学负载的基元功能材料。但受限于粉末尺寸小、活性高,目前鲜有关于多孔铜粉制备工艺的研究。以球磨后的铜锌合金粉末为前驱体,采用气相去合金的方法成功制备了多孔铜粉。应用SEM、EDS、XRD、TEM等表征手段研究了去合金温度、时间、原始合金成分和球磨变形对粉末性能的影响。实验结果表明,孔隙结构变化是Zn原子去合金驱动力,Cu原子表面扩散和Cu原子体扩散三者互相竞争的结果。表面孔隙粗化过程受Cu原子表面扩散主导,而Cu原子体扩散会引起孔隙结构的收缩。球磨引入的位错通过提供快速扩散通道的方式降低了孔隙粗化过程的扩散激活能,加快了去合金过程的进行。制备的多孔粉末最大表面孔隙率为17%,平均孔隙尺寸为0.6～1.1μm。通过调整工艺参数,可以调控多孔铜粉的表面孔隙。     

脱合金法制备纳米多孔金研究进展

纳米多孔金作为一种重要的结构功能材料,在过滤、催化剂载体、传感器、光催化、微流体及分离等方面有着巨大的应用前景。文章综述了纳米多孔金的制备方法。一脱合金法以及最新进展,介绍了脱合金的原理、纳米多孔金的性能以及将来的应用领域     

腐蚀添加剂对Cu-Mn合金制备孔径可控纳米多孔铜的影响

以铜锰单相固溶体为前躯体合金,利用去合金化法,在盐酸腐蚀液中添加适量不同的络合剂、金属盐可制备出成分纯净、孔形貌可控的三维连通纳米多孔铜(NPC)。采用X射线衍射仪(XRD)、扫描电镜能谱(SEM-EDS)、图像分析软件(Image-Pro Plus)对样品的物相、组分、微观形貌和平均孔径尺寸进行表征。结果表明：腐蚀添加剂的种类和浓度对孔结构形成过程和孔形貌具有重要影响。与未添加络合剂相比,添加硫脲、柠檬酸等络合剂后,腐蚀后的样品的孔径和韧带尺寸都发生不同程度的细化,络合常数越大,铜原子表面扩散系数越小,细化效果越明显;添加硫脲后能显著细化多孔结构,NPC平均韧带尺寸可在18～90 nm之间调控,且其浓度越高,孔径、韧带尺寸越小;添加适量金属盐Fe₂(SO₄)₃、CuSO₄、ZnSO₄后腐蚀液中出现副反应,反应速率大幅度提高,孔结构发生粗化,出现韧带尺寸分布呈纳米级和微米级共存的多孔结构,当CuSO₄添加浓度超过20 mmol/L时,多孔样品断裂截面失去初...     

脱合金法制备Fe基纳米多孔材料及其催化性能

近年来,纳米多孔金属材料成为催化和传感器等领域的研究热点。本研究将铁基非晶合金和脱合金工艺相结合,制备具有催化性能的纳米多孔材料。采用真空感应熔炼装置和真空急冷甩带装置制备宽1mm×厚25μm的Fe_(60)Pd_(20)P_(20)非晶合金条带,并借助X射线衍射仪(XRD)、扫描电镜(SEM)、能谱仪(EDS)对非晶合金条带进行表征。将Fe60Pd_(20)P_(20)非晶合金作为电化学脱合金的前驱体材料,在25℃、1mol/L H_2SO4电解液中进行1h恒电位脱合金处理,成功制备出具有均匀三维连通孔道结构的纳米多孔金属材料。经电化学测试表明,恒电位0.72V获得的纳米多孔材料,在0.5mol/L H_2SO4+0.5mol/L HCOOH溶液的循环伏安曲线中,较原非晶合金的氧化峰电压负移约0.4V,氧化峰电流密度提高约15倍,该纳米多孔材料对甲酸的分解有明显的催化性能。     

脱合金化法制备纳米多孔铂合金的研究进展

纳米多孔金属由纳米尺度的孔隙和金属韧带组成,具有三维双连通的网络状结构,兼具纳米材料和金属材料的双重特性,在催化、传感和药物输送等领域具有广阔的应用前景。脱合金化法操作简单,工艺流程短,成本相对较低,是制备纳米多孔金属的常用方法。目前,利用脱合金化法制备的纳米多孔Pt合金因其对甲醇氧化和氧还原反应具有优异的催化活性而备受关注,有望在燃料电池等相关领域实现应用。近年,研究学者不断丰富纳米多孔Pt合金的合金体系,通过优化合金成分和脱合金化工艺对其结构和性能进行调控,发展出多种形态的纳米多孔Pt合金,系统调查了前驱体的结构和成分、脱合金工艺参数对纳米多孔Pt合金的组织结构、形貌和性能的影响,并对纳米多孔形成和优异性能的机理进行了广泛的研究。利用脱合金化法制备的纳米多孔Pt合金具有多种形态,如低维的纳米颗粒、纳米花、纳米线和薄膜以及三维的纳米多孔带材等。低维的纳米多孔Pt合金因其更大的比表面积和纳米尺寸效应而具有更为突出的催化活性,而三维的纳米多孔带材具有均匀的纳米多孔结构,且克服了低维合金易团聚的问题。通过调整前驱体合金的化学成分和组织结构,改变脱合金化工艺参数,以及对纳米多孔合金进行退火处...     

合金成分对Ag-Cu二元合金制备纳米多孔银的影响

本文研究了纳米多孔银的制备及合金成分对纳米多孔银微观结构的影响。选用Ag含量(原子百分数)为15%,20%和25%(分别对应亚共晶,共晶与过共晶成分)的Ag-Cu合金薄带,通过化学去合金法制得具有三维的,韧带-孔洞双连续结构的纳米多孔银。利用X射线衍射仪(XRD)与扫描电子显微镜(SEM)对试样进行物相组成和微观结构的观察与分析。研究了Cu含量的变化对纳米多孔银微观结构及性能的影响。得出结论:去合金介质及温度等腐蚀条件一定的情况下,去合金时间越长,纳米多孔银的韧带尺寸越大。在腐蚀介质和温度等条件相同的情况下,纳米多孔结构特征尺寸受合金成分影响,Cu含量越高,去合金过程中产生的孔洞/通道尺寸越大。由于Cu含量不同,Ag15Cu85,Ag20Cu80和Ag25Cu80三种成分的合金中,Ag20Cu80去合金化得到的纳米多孔Ag的韧带孔洞微观结构最均匀。     

去合金化制备纳米多孔金属材料的研究进展

用去合金化制备的孔隙尺寸小于100nm的纳米多孔金属材料,开拓了多孔金属材料一个新的应用领域.目前的研究主要集中于通过不同的合金体系制备出不同的纳米多孔金属,分别介绍了纳米多孔金、铂、铜、钯、钛的制备工艺,并对孔洞形成的溶解-再沉积机制、体扩散机制、表面扩散机制、渗流机制及相分离模型进行了简述.对纳米多孔金的现有研究表明,纳米多孔金具有良好的化学稳定性、高的比表面积以及高的屈服强度,目前应用研究包括作为热交换器、传感器及催化材料等方面.     

脱合金法制备纳米多孔镍材料研究进展

纳米多孔金属镍材料的研制成功,开拓了多孔金属新的应用领域。综述了脱合金法从Ni—Al合金中制备纳米多孔镍材料的必要条件,并十分析了脱元素法和脱相法各自的特点。脱元素法获得的纳米多孔镍的结构是三维无序内部互连通孔结构,而脱相法会产生原有的γ相或γ’相与多孔结构互相交织的网状结构,其中互通孔道大多为几百纳米宽。脱相法是个电化学控制的过程,脱元素法不需要加电压。同时,指出了纳米多孔镍基材料的应用领域及今后的研究方向。     

纳米多孔金属的制备方法研究进展

综述了去合金化法和模板法2种制备纳米多孔金属材料的方法.以多孔金的制备为代表.进行了较详细的介绍.比较2种制备方法得出,模板法简单方便、可控性良好,应用更加广泛;模板法包括AAO模板/PC模板法、蛋白石/反蛋白石结构模板法以及氢气模板法等.通过模板法能够获得分布有序的多孔结构,且孔间的联通性较好,是一种制备纳米多孔材料的重要方法.     

脱合金化制备纳米多孔Ni-Fe合金及其电催化性能

采用真空熔炼与固溶相结合的方法获得原子分数为Ni_30-xFe_xMn₇₀(x=0,10,20)的前驱体合金,通过脱合金化方法制备纳米多孔Ni及Ni-Fe合金,采用X射线衍射(XRD)、扫描电子显微镜(SEM)分析合金相组成和微观结构,运用线性扫描伏安法、交流阻抗、方波电位法及计时电位法研究电极的析氢电催化性能。结果表明:加入Fe获得了片状结构的纳米多孔Ni-Fe合金,提高了纳米多孔Ni的表面积,且Fe与Ni产生协同效应,能够有效提高合金的析氢电催化活性。当Fe含量为10%(原子分数)时,脱合金化得到的纳米多孔Ni-Fe合金表面积最大,析氢电催化性能最好,在0.1A/cm^2电流密度下,析氢过电位仅56mV,经10h连续电解,表现出良好的电催化活性和电化学稳定性。     

Relationship between dealloying conditions and coarsening behaviors of nanoporous copper fabricated by dealloying Cu-Ce metallic glasses

Monolithic nanoporous copper(NPC) with tunable ligament size(107–438 nm) was synthesized by dealloying a new Cu-Ce binary glassy precursor in dilute H_2SO_4 aqueous solution. The effects of the dealloying conditions on the morphologies of NPC were evaluated comprehensively. The results show that the ligaments of NPC can significantly coarsen with the increase of acid concentration, elevation of reaction temperature or prolongation of immersion time. These coarsening behaviors can be well described by a diffusion based growth kinetic model. Moreover, the surface diffusivity and activation energy for diffusion of Cu atoms were also estimated to investigate the formation mechanism of NPC, which is mainly governed by dissolution of Ce element in the glassy precursor coupled with nucleation and growth of Cu clusters via the precursor/solution interface. In the experiment of the degradation of methyl orange(MO) dye, the NPC fabricated by Cu-Ce metallic glasses exhibits superior sono-catalytic activity.     

General synthesis of sponge-like ultrafine nanoporous metals by dealloying in citric acid

A general method is proposed to synthesize ultrafine nanoporous Cu,Ag,and Ni with novel sponge-like morphologies,high porosities,and large surface areas.The materials are produced by dealloying Mg65M25Y10 (M =Cu,Ag,and Ni) metallic glasses in citric acid.Citric acid played a key role due to its capping effect,which reduced the surface diffusion of metals.A structural model consistent with the sponge-like morphology was constructed to calculate the porosity and the surface area.The mechanism of the dealloying process in dtric add,involving ligament formation and coarsening,was illustrated.The mechanism was capable of explaining the experimental trends of dealloying,especially the morphology.A glucose sensor,which can be further developed into a high-precision real-time glucose monitor for medical use,was constructed using sponge-like nanoporous copper.Our findings are not only relevant to understanding the dealloying mechanism of metallic glasses,but also provide promising materials for multiple applications.     

溶胶-凝胶法制备宽带减反膜

为了克服单层减反射膜剩余反射高，色彩还原性能差的缺点，需要制备宽带减反膜。纳米多孔SiO2薄膜可以实现很好的宽带减反效果。本文用光学薄膜设计程序模拟了光学参数的变化对薄膜光学性能的影响，优化了薄膜的光学参数。实验上通过酸碱两步法和溶胶-凝胶技术制备了折射率梯度的纳米多孔SiO2宽带减反膜。采用椭偏仪、FE-SEM、紫外-可见分光光度计等方法研究薄膜的光学特性和表面形貌。结果表明实验制备的SiO2薄膜具有可控的纳米多孔结构，折射率在1．18～1．43之间可连续调节。形成的宽带减反膜在可见光区域的平均反射率仅为0．44％。     

Preparation of copper and silicon/copper powders by a gas evaporation-condensation method

Pure and silicon-coated metal copper nano to submicron-sized powders were prepared by gas evaporation and condensation. This powder was synthesized by using an industrial electron accelerator, ELV-6, with Ar as the carrier gas. Vapour from the liquefied metal surface was transferred to the cold zone by the carrier gas and precipitated as spherical Cu metal and Si/Cu composite powders. The mean diameter of the resulting powder was 100–200 nm.     

The preparation of nanoporous gold electrodes by electrochemical alloying/dealloying process at room temperature and its properties

A novel method of preparing nanoporous gold has been developed: nanoporous gold materials have been prepared on the bulk gold substrates by galvanostatic electrochemical alloying and galvanostatic electrochemical dealloying processes at 0.05 mA in 1 M LiPF₆, EC/DMC(1:1, v/v) solution at room temperature. The result shows that the particle size ranges from 50 nm to 100 nm on the surface of the prepared nanoporous gold by Quanta 200FEG scanning electron microscope. And it is determined that the maximum anodic current for the nanoporous gold electrode is 50 times higher than that of the polished gold electrode in 0.5 M KOH by the cyclic voltammograms.     

Nanoporous copper sonocatalysts prepared by dealloying Cu–Al–Ti amorphous ribbons

ABSTRACT

Nanoporous copper (NPC) with a controllable ligament width was prepared by chemically dealloying Cu₄₅Al₄₅Ti₁₀ amorphous ribbons in dilute HCl solution. X-ray diffraction and scanning electron microscopy analysis confirmed the 3D, bicontinuous, nanoporous structure constituting fcc-Cu ligaments of 39–79?nm thickness. The coarsening of NPC ligaments increased significantly with an increase of HCl concentration, reaction temperature or time. The surface diffusivity and activation energy of NPC were also calculated. Finally, the catalytic activity of NPC was validated with the ultrasound and H₂O₂-assisted degradation of methyl orange (MO), where 99% MO was degraded within 15?min.     

Preparation of copper nanoparticles on carbon nanotubes by electroless plating method

Densely distributed copper nanoparticles have been deposited on the surface of carbon nanotubes with a size of ∼10 nm by the electroless plating method. It has been found that the pretreatment of the carbon nanotubes is very important to obtain the copper nanoparticles on the carbon nanotubes; in our experiments, one-step pretreatment of mixed HNO₃ and H₂SO₄ was found effective. In order to attain nanosized copper particles, the electroless plating parameters should be closely controlled; e.g., the pH value of the plating solution, the temperature, and the concentration and titrating speed of HCOH were critical.     

次亚磷酸钠还原法制备纳米铜颗粒

利用液相还原两步法,油酸为萃取荆和保护剂,葡萄糖和次亚磷酸钠将五水硫酸铜分别还原为氧化亚铜和单质铜,制备得到了粒度为50～100nm左右分散均匀的球形纳米铜颗粒,并用XRD、SEM和TEM对其进行了表征.结果表明,在油酸的保护下,采用液相还原两步法可制得分散性好、具有抗氧化性能的球形纳米铜颗粒.     

纳米多孔二氧化硅薄膜的制备与表征

以正硅酸乙酯为原料,采用酸/碱两步溶胶 凝胶法、结合匀胶和超临界干燥等工艺在硅片上成功制备了纳米多孔二氧化硅薄膜。适合匀胶的二氧化硅溶胶的粘度范围为 9~15mPa·s;多孔二氧化硅薄膜表面均匀平整,其厚度为400~1000nm;折射率为1.09~1.24;介电常数为1.5~2.5。该多孔二氧化硅薄膜具有三维网络结构,二氧化硅微粒直径为10~20nm。