Dealloying to Nanoporous Silver and Its Implementation as a Template Material for Construction of Nanotubular Mesoporous Bimetallic Nanostructures

Nanoporous silver (NPS) is fabricated by selectively dissolving Al from AgAl alloys in corrosive electrolytes at room temperature. Electron spectroscopy characterizations demonstrate that the NaOH electrolyte is beneficial to the formation of a three‐dimensional bicontinuous porous nanostructure with uniform and tunable pore and ligament dimensions of a few tens of nanometers, while processing in HCl electrolyte easily lead to coarsened porous nanostructures. The high‐surface‐area Ag nanostructures are demonstrated as novel effective template materials to the construction of nanotubular mesoporous Pt/Ag and Pd/Ag alloy structures, which are realized via room temperature galvanic replacement reactions with H₂PtCl₆ and K₂PdCl₄ solutions by adding a high concentration of Cl^? ions as a coordinating agent. Electrochemical measurements indicate that the resulting hollow and porous bimetallic nanostructures show enhanced electrocatalytic activities and CO‐tolerance with better durability toward methanol and formic acid oxidation due to alloying with Ag.     

金纳米粒子的合成、特性及其在生物医学检测中的应用研究进展

近年来,纳米技术越来越广泛的应用到各个领域,金纳米粒子因其具有许多优良的物理、化学及生物学性质而引起了人们特别的关注。本文综述了金纳米粒子几种经典的合成方法,以及基于金纳米粒子独特的理化性质在病原体、核酸蛋白质检测方面的最新研究进展。     

Silver versus gold catalysis in tandem reactions of carbonyl functions onto alkynes: a versatile access to furoquinoline and pyranoquinoline cores

An efficient and versatile tandem process of acetalization and cycloisomerization reactions has been developed for the reactions of 1-alkynyl-2-carbonylquinoline substrates. The reaction occurs thanks to Au(I) and Ag(I) catalysis. Silver(I) catalysis has been extensively studied (11 different silver species) on a broad range of quinoline derivatives (variation of alkyne substituent, of carbonyl function and of nucleophiles), leading to a variety of furoquinoline and pyranoquinoline moieties. An insight is given for the presumed mechanism along with DFT-B3 LYP/6-31G** calculations to address the 6-endo and 5-exo regioselectivities observed.     

Investigations of the catalytic properties of manganese oxides for the oxygen reduction reaction in alkaline media

The oxygen reduction reaction (ORR) was studied in KOH electrolyte on different manganese oxides, dispersed on a carbon powder (MnO_x/C). The oxides were prepared by different methods, for producing MnO, Mn₃O₄ and MnO₂ as major phases dispersed on the Vulcan XC-72 carbon. The oxides were characterized by XRD (X-ray diffraction) and in situ XANES (X-ray absorption near edge structure). The electrochemical measurements were made using cyclic voltammetry and steady state polarization curves carried out in an ultra-thin layer rotating ring/disk electrode. The results have shown lower activity for the ORR on the MnO_x/C species compared to that on Pt/C, but higher activity compared to that of pure Vulcan carbon. Formation of involving 2e⁻ per O₂ molecule is the main path of the ORR in the studied MnO_x/C catalysts but, at low overpotentials and rotation rates the number of electrons is raised to 4 due to the occurrence of a disproportionation reaction. Large differences of electrocatalytic activity were seen for the different oxide species, and these were related to the presence of a Mn(IV) phase and the occurrence of a mediation processes involving the reduction of Mn(IV) to Mn(III), followed by the electron transfer of Mn(III) to oxygen.     

Facile synthesis of nitrogen-doped carbon nanosheets as metal-free catalyst with excellent oxygen reduction performance in alkaline and acidic media

Journal of Solid State Electrochemistry - In this work, a low-cost, high-performance, and environmentally friendly metal-free electrocatalyst based on N-doped carbon nanosheets (NCNs) was...     

快速微波法制备掺氮石墨烯用于碱性氧还原电催化剂

采用微波法在氨气气氛下快速加热石墨烯（G）制备了含氮量在4.05 wt%-5.47 wt%的掺氮石墨烯（NG）. 将上述的掺氮石墨烯用作碱性电解质条件下的氧还原电催化剂,起始还原电势为0.17 V（vs SHE）,接近商用碳载铂催化剂的0.21 V（vs SHE）. 采用透射电子显微镜、拉曼光谱和X射线光电子能谱研究了掺氮石墨烯的形貌、结构和掺杂氮原子的键合方式. 结果发现,掺氮石墨烯的氧还原起始电位随着石墨氮原子含量的提高而上升,说明石墨类型的氮含量是影响其氧还原催化活性的关键因素. 实验结果表明,微波法快速制备的掺氮石墨烯在碱性条件下表现出较高的氧还原催化活性,具有作为碱性燃料电池阴极催化剂的潜力.     

Green Silver and Gold Nanoparticles: Biological Synthesis Approaches and Potentials for Biomedical Applications

The nanomaterial industry generates gigantic quantities of metal-based nanomaterials for various technological and biomedical applications; however, concomitantly, it places a massive burden on the environment by utilizing toxic chemicals for the production process and leaving hazardous waste materials behind. Moreover, the employed, often unpleasant chemicals can affect the biocompatibility of the generated particles and severely restrict their application possibilities. On these grounds, green synthetic approaches have emerged, offering eco-friendly, sustainable, nature-derived alternative production methods, thus attenuating the ecological footprint of the nanomaterial industry. In the last decade, a plethora of biological materials has been tested to probe their suitability for nanomaterial synthesis. Although most of these approaches were successful, a large body of evidence indicates that the green material or entity used for the production would substantially define the physical and chemical properties and as a consequence, the biological activities of the obtained nanomaterials. The present review provides a comprehensive collection of the most recent green methodologies, surveys the major nanoparticle characterization techniques and screens the effects triggered by the obtained nanomaterials in various living systems to give an impression on the biomedical potential of green synthesized silver and gold nanoparticles.     

Co3O4/聚吡咯/石墨烯碱性溶液中电化学还原氧

燃料电池具有较高的能量密度和发电效率,以清洁能源为原料,零污染排放,是一种具有发展前景的能量储存和转化装置.阴极氧还原反应(ORR)在燃料电池中起着关键作用.ORR广泛采用贵金属铂基催化剂,但是它们价格昂贵,电子动力学转移速率慢,碱性条件下易团聚,这些亟需解决的问题阻碍了燃料电池商业化进程.近期,一些非贵金属催化剂被广泛研究,例如氮掺杂碳材料、Fe/N/C和Co/N/C材料等,它们有可能在未来替代铂基催化剂.我们的目标是合成新型高催化活性的Co/N/C及其衍生非贵金属材料,用于ORR催化反应.由于石墨烯具有独特的形貌、较大的比表面积和良好的导电性,其表面含有功能化的官能团,所以我们选择石墨烯作为碳载体.首先,用改性休克尔方法合成了氧化石墨烯(GO),为了提高其催化活性,采用聚吡咯作为氮源对其进行了氮掺杂,制备了聚吡咯/氧化石墨烯(Ppy/GO).通过ORR催化性能测试发现,GO对ORR具有一定的催化活性,它的起始电位和阴极电流电位分别为–0.31 V vs SCE和–0.38 V vs SCE;Ppy/GO的起始电位和阴极电流电位分别为–0.20 V vs SCE和–0.38 V vs SCE,氮掺杂对GO的催化活性有所提高.采用水热法沉积氧化钴合成了Co3O4/聚吡咯/氧化石墨烯(Co3O4/Ppy/GO).其形貌为Co3O4分散在氮掺杂GO表面.在KOH电解质(0.1 mol/L)中测试,Co3O4/Ppy/GO的起始电位和阴极电流电位分别为–0.20 V和–0.38 V vs SCE.经过800℃高温煅烧处理后,Co3O4/Ppy/GO-800的催化活性明显提高,起始电位和阴极电流电位分别达到–0.10 V和–0.18 V vs SCE.ORR电子转移数为3.4,接近于4电子反应途径.Co3O4/Ppy/GO对ORR的催化活性及4电子催化选择性较高,可能是由于纳米形态的Co3O4和Ppy/GO之间具有较强的表面作用力,聚吡咯掺杂的氧化石墨烯具有较强的电子储存及释放能力.综上,我们通过水热法制备了钴、氮共掺杂的GO,并研究了其对ORR的催化活性和电子转移选择性.结果表明Co3O4/Ppy/GO是一种高效的非贵金属电催化剂,在碱性电解质中具有很高的ORR催化活性,在燃料电池阴极催化剂方面很有前景.     

Electrocatalytic activity of dispersed platinum and silver alloys and manganese oxides for the oxygen reduction in alkaline electrolyte

This work reviews the studies conducted in this laboratory of the oxygen reduction reaction (ORR) on electrocatalysts formed by Pt-M/C (M = V, Cr, Co) and Ag-Pt/C alloys and on different Mn oxides (MnO/C, Mn₃O₄/C, MnO₂/C) in KOH electrolyte. The physical and electronic properties of the materials are investigated by in situ XAS (x-ray absorption spectroscopy) in the XANES (x-ray absorption near edge structure) region. The electrocatalytic activity for the ORR on the different catalysts is compared through mass-transport-corrected Tafel plots. The XANES results for the Pt-M/C and Ag-Pt/C composites at high electrode potentials show lower vacancy of the Pt 5d band compared to pure Pt/C, while for the results indicate a chance of the Mn oxidation state as a function of the electrode potential. The electrochemical measurements evidence increased electrocatalytic activity of the Pt alloys compared to pure Pt and this is attributed to a lowering of the adsorption strength of adsorbed oxygen species caused by the reduced Pt reactivity. An activity enhancement of the Ag atoms on the Ag-Pt/C alloys compared to pure Ag is ascribed to an electronic effect induced by the presence of Pt, increasing the Ag-O adsorption strength. In the case of the Mn_yO_x/C materials, the electrochemical results show low activity for MnO/C and higher activity for MnO₂/C and Mn₃O₄/C. This is explained based on the activation for the ORR, which is higher for the material with higher MnO₂ contents and the occurrence of a mediation processes involving the reduction of Mn(IV) to Mn(III), followed by the electron transfer of Mn(III) to oxygen. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 12, pp. 1417–1426. Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes,” October 18–22, 2005, Moscow. The text was submitted by the authors in English.     

原位水热合成Ce(Ⅳ)-X分子筛及对噻吩的吸附性能

通过原位水热合成方法直接制备出不同载Ce量的Ce(Ⅳ)-X分子筛,并考察了其对模拟汽油中噻吩的吸附性能。采用粉末X射线衍射(XRD)、傅里叶变换红外(FT-IR)、紫外-可见漫反射(UV-vis DRS)、全谱直读等离子体原子发射光谱(ICP-AES)、氮气吸附和NH₃程序升温热脱附(NH₃-TPD)等方法对分子筛进行表征。结果表明,合成分子筛均具备典型的X型分子筛结构,同时Ce(Ⅳ)被较好地引入到分子筛的骨架结构中;载Ce分子筛的酸性大于X分子筛,而且Ce(Ⅳ)-X分子筛的酸性随着Ce掺杂量的增加而增强。吸附实验表明,载Ce分子筛对噻吩的吸附性能明显好于X分子筛。其中,n(Ce)/n(Si)=0.05的分子筛脱硫效果最佳,饱和吸附容量达到52.541 9 mg/g。再生实验表明,加热再生的Ce(Ⅳ)-X分子筛对噻吩仍具有理想的吸附效果。n(Ce)/n(Si)=0.05的分子筛再生后饱和吸附容量为47.512 1 mg/g,约为新鲜吸附剂的90.43％。     

Fe2 and Fe4 clusters encapsulated in vacant polyoxotungstates: hydrothermal synthesis, magnetic and electrochemical properties, and DFT calculations

While the reaction of [PW(11)O(39)](7-) with first row transition-metal ions M(n+) under usual bench conditions only leads to monosubstituted {PW(11)O(39)M(H(2)O)} anions, we have shown that the use of this precursor under hydrothermal conditions allows the isolation of a family of novel polynuclear discrete magnetic polyoxometalates (POMs). The hybrid asymmetric [Fe(II)(bpy)(3)][PW(11)O(39)Fe(2) (III)(OH)(bpy)(2)]12 H(2)O (bpy=bipyridine) complex (1) contains the dinuclear {Fe(micro-O(W))(micro-OH)Fe} core in which one iron atom is coordinated to a monovacant POM, while the other is coordinated to two bipyridine ligands. Magnetic measurements indicate that the Fe(III) centers in complex 1 are weakly antiferromagnetically coupled (J=-11.2 cm(-1), H=-JS(1)S(2)) compared to other {Fe(micro-O)(micro-OH)Fe} systems. This is due to the long distances between the iron center embedded in the POM and the oxygen atom of the POM bridging the two magnetic centers, but also, as shown by DFT calculations, to the important mixing of bridging oxygen orbitals with orbitals of the POM tungsten atoms. The complexes [Hdmbpy](2)[Fe(II)(dmbpy)(3)](2)[(PW(11)O(39))(2)Fe(4) (III)O(2)(dmbpy)(4)]14 H(2)O (2) (dmbpy=5,5'-dimethyl-2,2'-bipyridine) and H(2)[Fe(II)(dmbpy)(3)](2)[(PW(11)O(39))(2)Fe(4) (III)O(2)(dmbpy)(4)]10 H(2)O (3) represent the first butterfly-like POM complexes. In these species, a tetranuclear Fe(III) complex is sandwiched between two lacunary polyoxotungstates that are pentacoordinated to two Fe(III) cations, the remaining paramagnetic centers each being coordinated to two dmbpy ligands. The best fit of the chi(M)T=f(T) curve leads to J(wb)=-59.6 cm(-1) and J(bb)=-10.2 cm(-1) (H=-J(wb)(S(1)S(2)+S(1)S(2*)+S(1*)S(2)+S(1*)S(2*))-J(bb)(S(2)S(2*))). While the J(bb) value is within the range of related exchange parameters previously reported for non-POM butterfly systems, the J(wb) constant is significantly lower. As for complex 1, this can be justified considering Fe(w)--O distances. Finally, in the absence of a coordinating ligand, the dimeric complex [N(CH(3))(4)](10)[(PW(11)O(39)Fe(III))(2)O]12 H(2)O (4) has been isolated. In this complex, the two single oxo-bridged Fe(III) centers are very strongly antiferromagnetically coupled (J=-211.7 cm(-1), H=-JS(1)S(2)). The electrochemical behavior of compound 1 both in dimethyl sulfoxide (DMSO) and in the solid state is also presented, while the electrochemical properties of complex 2, which is insoluble in common solvents, have been studied in the solid state.     

QbD approached comparison of reaction mechanism in microwave synthesized gold nanoparticles and their superior catalytic role against hazardous nirto‐dye

Microwave irradiation (MI) process characteristically enables extremely rapid “in‐core” heating of dipoles and ions, in comparison to conventional thermal (conductance) process of heat transfer. During the process of nanoparticles synthesis, MI both modulates functionality behaviors as well as dynamic of reaction in favorable direction. So, MI providing a facile, favorable and alternative approach during nanoparticles synthesis nanoparticles with enhanced catalytic performances. Although, conventionally used reducing and capping reagents of synthetic origin, are usually environmentally hazardous and toxic for living organism. But, in absence of suitable capping agent; stability, shelf life and catalytic activity of metallic nanoparticles adversely affected. However, polymeric templates which emerged as suitable choice of agent for both reducing and capping purposes; bearing additional advantages in terms of catalyst free one step green synthesis process with high degree of biosafety and efficiency. Another aspect of current works was to understand role of process variables in growth mechanism and catalytic performances of microwave processed metallic nanoparticles, as well as comparison of these parameters with conventional heating method. However, due to poor prediction ability with previously published architect OFAT (One factor at a time) design with these nanoparticles as well as random selection of process variables with their different levels, such comparison couldn't be possible. Hence, using gum Ghatti (Anogeissus latifolia) as a model bio‐template and under simulated reaction conditions; architect of QbD design systems were integrated in microwave processed nanoparticles to establish mechanistic role these variables. Furthermore, in comparison to conventional heating; we reported well validated mathematical modeling of process variables on characteristic of nanoparticles as well as synthesized gold nanoparticles of desired and identical dimensions, in both thermal and microwave‐based processes. Interestingly, despite of identical dimension, MI processed gold nanoparticles bearing higher efficiency (kinetic rate) against remediation of hazardous nitro dye (4‐nitrophenol), into safer amino (4‐aminophenol) analogues.     

Gold(I)‐Catalyzed Asymmetric Desymmetrization of meso‐Alkynyl Diols and Kinetic Resolution of the Corresponding dl‐Diols: Effects of Celite Filtration and Silver Salts

The asymmetric desymmetrization of meso‐2‐alkynylbenzenediols through the use of a combination of axially chiral diphosphine(AuCl)₂ precatalysts and silver salt co‐catalysts gave optically active isochromene compounds with high enantioselectivities in good yields. The corresponding dl ‐diol isomers underwent efficient kinetic resolution to give the cyclized isochromenes and recovered diols with high enantioselectivities under similar conditions. The high reactivity and selectivity in the desymmetrization of the meso‐diols is independent of the combination of axially chiral diphosphine(AuCl)₂ precatalyst and silver salt co‐catalyst, whereas the corresponding tricarbonylchromium complexes of alkynylbenzenediols were affected by the combination of the diphosphine(AuCl)₂ and silver salt. The reactivity was largely dependent on the nature of the gold(I) species.     

Hydrothermal fabrication of quasi-one-dimensional single-crystalline anatase TiO2 nanostructures on FTO glass and their applications in dye-sensitized solar cells

One-dimensional and quasi-one-dimensional semiconductor nanostructures are desirable for dye-sensitized solar cells (DSSCs), since they can provide direct pathways for the rapid collection of photogenerated electrons, which could improve the photovoltaic performance of the device. Quasi-1D single-crystalline anatase TiO(2) nanostructures have been successfully prepared on transparent, conductive fluorine-doped tin oxide (FTO) glass with a growth direction of [101] through a facile hydrothermal approach. The influences of the initial titanium n-butoxide (TBT) concentration, hydrothermal reaction temperature, and time on the length of quasi-1D anatase TiO(2) nanostructures and on the photovoltaic performance of DSSCs have been investigated in detail. A power conversion efficiency of 5.81% has been obtained based on the prepared TiO(2) nanostructure photoelectrode 6.7 μm thick and commercial N719 dye, with a short-circuit current density of 13.3 mA cm(-2) , an open-circuit voltage of 810 mV, and a fill factor of 0.54.     

Cobalt and nitrogen codoped porous carbon as superior bifunctional electrocatalyst for oxygen reduction and hydrogen evolution reaction in alkaline medium

Metal (cobalt)/nitrogen codoped carbon was first fabricated by pyrolysis of coordinated “noncarbonizable” polymer as bifunctional catalyst for ORR and HER, which showed better electrocatalytic performances than most bifunctional doped carbon catalysts in alkaline electrolyte.     

Activity–Structure Correlation of Pt/Ru Catalysts for the Electrodecomposition of Methanol: The Importance of RuO2 and PtRu Alloying

Bimetallic catalysts: The effect of PtRu alloying and the influence of RuO₂ species on the methanol oxidation activity of PtRu/C catalysts is studied. Different heat treatments—utilizing either N₂ or air—are applied to the bimetallic materials to enhance the degree of alloying or produce RuO₂ (see picture). The catalysts with the best performance are characterized by a small particle size, a high degree of PtRu alloying, and the presence of a Pt‐related species on their surface.