Novel flexible chemical gas sensor based on poly(3,4-ethylenedioxythiophene) nanotube membrane

Poly(3,4-ethylenedioxythiophene) nanotubes (PEDOT NTs) flexible membrane was successfully fabricated by vapor deposition polymerization (VDP) mediated electrospinning for ammonia gas detection. PVA nanofibers (NFs) were electrospun as a core part and polyvinyl alcohol (PVA)/PEDOT coaxial nanocables (NCs) were prepared by VDP method via EDOT monomer adsorption onto the electrospun PVA NFs as templates. To obtain the PEDOT NTs membrane, the PVA NFs were removed from PVA/PEDOT coaxial NCs with distilled water. PVA/PEDOT coaxial NCs and PEDOT NTs had the conductivities of 71 and 61 S cm⁻¹ and were applied as a transducer for ammonia gas detection in the range of 1-100 parts per million (ppm) of NH₃ gas. They exhibited the minimum detectable level of ca. 5 parts per million (ppm) and fast response time (less than 1 s) towards ammonia gas. In a recovery time, the PEDOT NTs membrane sensor was ca. 30 s and shorter compared to that of the membrane sensor based on the PVA/PEDOT NCs (ca. 50 s). In addition, sensor performance of PEDOT NTs membrane was also undertaken as a function of membrane thickness. Thick membrane sensor (30 μm) had the enhanced sensitivity and the sensitivity on the membrane thickness was in the order of 30 μm > 20 μm > 10 μm at 60 ppm of NH₃ gas.     

Colloidal Self‐Assembly of Catalytic Copper Nanoclusters into Ultrathin Ribbons

Metal nanoclusters (NCs) with diameter below 2 nm are promising catalysts in oxygen reduction reactions (ORR). However, the high surface energy of ultra‐small clusters leads to structural instability, shedding doubt on practical applications. Herein, we demonstrate a self‐assembly method to improve the durability of catalytic metal NCs, employing copper NCs capped by 1‐dodecanethiol (DT) to form free‐standing ribbons in colloidal solution. By tuning the cooperation between the dipolar attraction between Cu NCs and the van der Waals attraction between DT, the thickness of ribbons is adjusted to a single NC scale. Such free‐standing ribbons exhibit excellent catalytic activity and durability in ORR.     

Precisely Controlled Synthesis of Pt-Pd Octahedral Nanoframes as a Superior Catalyst towards Oxygen Reduction Reaction

Pt-based nanoframes represent a class of promising catalysts towards oxygen reduction reaction. Herein, we, for the first time, successfully prepared Pt-Pd octahedral nanoframes with ultrathin ridges less than 2 nm in thickness. The Pt-Pd octahedral nanoframes were obtained through site-selected deposition of Pt atoms onto the edge sites of Pd octahedral seeds, followed by selective removal of the Pd octahedral cores via chemical etching. Due to that a combination of three-dimensional opens geometrical structure and Pt-skin surface compositional structure, the Pt-Pd octahedral nanoframes/C catalyst shows a mass activity of 1.15 A/mg_Pt towards oxygen reduction reaction, 5.8 times enhancement in mass activity relative to commercial Pt/C catalyst (0.20 A/mg_Pt). Moreover, even after 8000 cycles of accelerated durability test, the Pt-Pd octahedral nanoframes/C catalyst still exhibits a mass activity which is more than three times higher than that of pristine Pt/C catalyst.     

Luminescent properties of pure cubic phase Y2O3/Eu3+ nanotubes/nanowires prepared by a hydrothermal method

One-dimensional pure cubic Y(2)O(3)/Eu(3+) nanocrystals (NCs) were synthesized by a hydrothermal method at various temperatures. The NCs prepared at 130 degrees C yielded nanotubes (NTs) with wall thickness of 5-10 nm and outer diameter of 20-40 nm. The NCs prepared at 170 and 180 degrees C yielded nanowires (NWs) with diameters of approximately 100 and approximately 300 nm, respectively. Their luminescent properties, including electronic transition processes, local environments surrounding Eu(3+) ions, electron-phonon coupling, and UV light irradiation induced spectral changes have been systematically studied and compared. The results indicate that the Y(2)O(3)/Eu(3+) NTs and NWs have strong red (5)D(0)-(7)F(2) transitions. The fluorescence lifetime of (5)D(1)-(7)F(1) hardly changes in different samples, while that of (5)D(0)-(7)F(2) decreases a small amount in Y(2)O(3)/Eu(3+) NTs. The (5)D(0)-(7)F(2) lines originate from the emissions of Eu(3+) ions occupying one C(2) site, like that in the bulk powders. The phonon sideline with a frequency shift of 40-50 cm(-1) appears at the low-energy side of the (7)F(0)-(5)D(0) zero phonon line. The relative intensity of the sideline to zero phonon line increases by varying from NTs to NWs, and the spectral position of the phonon sideline shifts red. The UV light irradiation induced spectral change in the charge-transfer band was studied. The results indicate that the spectral change is dependent on sample size and is wavelength selective. A detailed model was proposed to explain the light-induced spectral change.     

Facile Synthesis of PdCu Echinus‐Like Nanocrystals as Robust Electrocatalysts for Methanol Oxidation Reaction

Exploiting high‐performance and inexpensive electrocatalysts for methanol electro‐oxidation is conductive to promoting the commercial application of direct methanol fuel cells. Here, we present a facile synthesis of echinus‐like PdCu nanocrystals (NCs) via a one‐step and template‐free method. The echinus‐like PdCu NCs possess numerous straight and long branches which can provide abundant catalytic active sites. Owing to the novel nanoarchitecture and electronic effect of the PdCu alloy, the echinus‐like PdCu NCs display high electrocatalytic performance toward methanol oxidation reaction in an alkaline medium. The mass activity of echinus‐like PdCu NCs is 1202.1 mA mg_Pd^?1, which is 3.7 times that of Pd/C catalysts. In addition, the echinus‐like structure, as a kind of three‐dimensional self‐supported nanoarchitecture, endows PdCu NCs with significantly enhanced stability and durability. Hence, the echinus‐like PdCu NCs hold prospect of being employed as electrocatalysts for direct alcohol fuel cells.     

Silica–Polypyrrole Hybrids as High-Performance Metal-Free Electrocatalysts for the Hydrogen Evolution Reaction in Neutral Media

Constructing inorganic–organic hybrids with superior properties in terms of water adsorption and activation will lead to catalysts with significantly enhanced electrocatalytic activity in the hydrogen evolution reaction (HER) in environmentally benign neutral media. Herein, we report SiO₂–polypyrrole (PPy) hybrid nanotubes supported on carbon fibers (CFs) (SiO₂ /PPy NTs–CFs) as inexpensive and high-performance electrocatalysts for the HER in neutral media. Because of the strong electronic interactions between SiO₂ and PPy, the SiO₂ uniquely serves as the centers for water adsorption and activation, and accordingly promotes the HER. The metal-free SiO₂ /PPy NTs–CFs displayed high catalytic activity in the HER in neutral media, such as a low onset potential and small Tafel slope, as well as excellent long-term durability.     

Silica–Polypyrrole Hybrids as High‐Performance Metal‐Free Electrocatalysts for the Hydrogen Evolution Reaction in Neutral Media

Constructing inorganic–organic hybrids with superior properties in terms of water adsorption and activation will lead to catalysts with significantly enhanced electrocatalytic activity in the hydrogen evolution reaction (HER) in environmentally benign neutral media. Herein, we report SiO₂–polypyrrole (PPy) hybrid nanotubes supported on carbon fibers (CFs) (SiO₂ /PPy NTs–CFs) as inexpensive and high‐performance electrocatalysts for the HER in neutral media. Because of the strong electronic interactions between SiO₂ and PPy, the SiO₂ uniquely serves as the centers for water adsorption and activation, and accordingly promotes the HER. The metal‐free SiO₂ /PPy NTs–CFs displayed high catalytic activity in the HER in neutral media, such as a low onset potential and small Tafel slope, as well as excellent long‐term durability.     

Synthesis of octahedral Pt-Pd alloy nanoparticles for improved catalytic activity and stability in methanol electrooxidation

We report Pt-Pd nanoparticles synthesized by means of a polyol process with glycerol as a reducing agent. The Pt-Pd nanoparticles exhibit dominantly exposed {111} facets in octahedral shape with complete alloy formation between Pt and Pd. Furthermore, the octahedral Pt-Pd alloy catalysts show improved catalytic activity and stability in methanol electrooxidation.     

Electroless Deposition of Nickel Nanowire and Nanotube Arrays as Supports for Pt-Pd Catalyst for Ethanol Electrooxidation

Nickel nanowire and nanotube arrays as supports for Pt-Pd catalyst were prepared by electroless deposition with anodic aluminum oxide template. Pt-Pd composite catalyst was deposited on the arrays by displacement reaction. SEM images show that the nickel nanowires have an average diameter of 100 nm and the nickel nanotubes have an average inner diameter of 200 nm. EDS scanning reveals that elemental Pt and Pd disperse uniformly on the arrays. Cyclic voltammetry study indicates that the nickel nanotube array loaded with Pt-Pd possesses a higher electrochemical activity for ethanol oxidation than the nickel nanowire array with Pt-Pd.     

铂钯修饰聚N-乙酰苯胺膜电极对甲酸的电催化氧化

由电化学方法在石墨电极表面制备了规整多孔的纳米结构聚N-乙酰苯胺(PAANI)膜,并以其为载体制备了Pt-Pd/PAANI/C二元金属微粒修饰的聚合物复合膜电极.SEM和XRD研究结果表明,Pt、Pd微粒在PAANI膜中均匀分散,有效地改善了催化剂中贵金属的分散度和电极的结构.在0.5mol/L H2SO4+0.5mol/LHCOOH溶液中的循环伏安结果表明,Pt-Pd/PAANI/C电极在酸性溶液中电催化氧化甲酸的性能明显优于直接电沉积的Pt-Pd/C电极,且表现出较高的稳定性.     

Ru修饰Pd二十四面体纳米晶的合成及其甲醇电催化氧化性能

表面结构控制和表面异种金属修饰是调控催化剂反应性的重要方法。因此,我们结合高指数晶面结构的高反应性与表面修饰异种金属,合成具有{730}高指数晶面的钯二十四面体纳米晶,并通过循环伏安扫描电沉积法得到Ru修饰的钯二十四面体纳米晶。电化学测试结果表明,低的Ru覆盖度(θ_(Ru)=0.08)可显著提高对碱性介质中甲醇电氧化的催化性能。电化学原位红外光谱结果表明,少量Ru的修饰没有减少CO的生成,而是促进了低电位下甲醇氧化成甲酸根。     

Cu2+-doped polypyrrole nanotubes with promoted efficiency for peroxidase mimicking and electrochemical biosensing

A facile template together with doping strategy is presented to fabricate Cu²⁺-doped polypyrrole (Cu²⁺/PPy) nanotubes (NTs) as efficient mimicking peroxidase and electrocatalyst. PPy NTs were first prepared using electrospun polyacrylonitrile nanofibers as templates and subsequently doped with Cu²⁺ via a simple immersion strategy. The as-prepared Cu²⁺/PPy NTs not only exhibit an outstanding peroxidase-like catalytic efficiency but also possess an excellent electrocatalytic activity, which is used for the detection of glucose, displaying a great promise for biosensing applications. The good enzyme-like and electrochemical performances of Cu²⁺/PPy NTs are owing to the reduced Fermi level compared with bare PPy NTs, which is beneficial for promoting the electron transfer to the substrate. The novel Cu²⁺/PPy NTs are a novel type of enzyme mimics and electrocatalysts for potential bright applications in biotechnology and environment science.     

Polyoxometalate‐Mediated One‐Pot Synthesis of Pd Nanocrystals with Controlled Morphologies for Efficient Chemical and Electrochemical Catalysis

Polyoxometalates (POMs), as inorganic ligands, can endow metal nanocrystals (NCs) with unique reactivities on account of their characteristic redox properties. In the present work, we present a facile POM‐mediated one‐pot aqueous synthesis method for the production of single‐crystalline Pd NCs with controlled shapes and sizes. The POMs could function as both reducing and stabilizing agents in the formation of NCs, and thus gave a fine control over the nucleation and growth kinetics of NCs. The prepared POM‐stabilized Pd NCs exhibited excellent catalytic activity and stability for electrocatalytic (formic acid oxidation) and catalytic (Suzuki coupling) reactions compared to Pd NCs prepared without the POMs. This shows that the POMs play a pivotal role in determining the catalytic performance, as well as the growth, of NCs. We envision that the present approach can offer a convenient way to develop efficient NC‐based catalyst systems.     

质子交换膜燃料电池Pd修饰Pt/C催化剂的电催化性能

通过对Pt催化剂表面进行Pd修饰提高质子交换膜燃料电池阴极催化剂的氧还原反应(ORR)活性. 采用乙二醇还原法制备了不同比例的Pd修饰Pt/C催化剂. 透射电镜(TEM)和X射线衍射(XRD)测试结果表明, 制备的催化剂贵金属颗粒粒径主要分布在1.75～2.50 nm之间, 并均匀地分散在碳载体表面. 循环伏安方法(CV)研究表明Pd修饰Pt/C催化剂的电化学活性面积低于传统的Pt/C催化剂. 但通过旋转圆盘电极(RDE)测试研究发现, 制备的催化剂具有比传统Pt/C催化剂高的ORR活性.     

Self‐Supported FeP‐CoMoP Hierarchical Nanostructures for Efficient Hydrogen Evolution

Fabricating highly efficient electrocatalysts for electrochemical hydrogen generation is a top priority to relief the global energy crisis and environmental contamination. Herein, a rational synthetic strategy is developed for constructing well‐defined FeP?CoMoP hierarchical nanostructures (HNSs). In general terms, the self‐supported Co nanorods (NRs) are grown on conductive carbon cloth and directly serve as a self‐sacrificing template. After solvothermal treatment, Co NRs are converted into well‐ordered Co?Mo nanotubes (NTs). Subsequently, the small‐sized Fe oxyhydroxide nanorods arrays are hydrothermally grown on the surface of Co?Mo NTs to form Fe?Co?Mo HNSs, which are then converted into FeP?CoMoP HNSs through a facile phosphorization treatment. FeP?CoMoP HNSs display high activity for hydrogen evolution reaction (HER) with an ultralow cathodic overpotential of 33 mV at 10 mA cm^?2 and a Tafel slope of 51 mV dec^?1. Moreover, FeP?CoMoP HNSs also possess an excellent electrochemical durability in alkaline media. First‐principles density functional theory (DFT) calculations demonstrate that the remarkable HER activitiy of FeP?CoMoP HNSs originates from the synergistic effect between FeP and CoMoP.     

On-substrate, self-standing hollow-wall Pt and PtRu-nanotubes and their electrocatalytic behavior

We report on a versatile approach for preparing on-substrate, self-standing and hollow-wall nanotubes (NTs) of Pt and PtRu-alloys. The method takes advantage of wet chemically processed ZnO-NTs that are used as sacrificial templates for electrodeposition. The electrocatalytic activity of these Pt-based NTs is exemplary demonstrated on the electro-oxidation of methanol.     

柴油尾气DOC催化剂Pt-Pd/CeO2的活性和抗硫性

采用浸渍法制备了不同Pt、Pd比例的Pt-Pd/CeO₂催化剂,考察了其催化氧化模拟柴油车尾气的活性,并测试了抗硫性。活性测试结果表明,Pt、Pd协同降低了催化剂的起燃温度,其比例对催化剂性能影响很大,其中,Pt_0.2Pd_0.8/CeO₂催化剂在模拟柴油车尾气(丙烯(C₃H₆)、一氧化碳(CO)和一氧化氮(NO))中的催化活性最高;C₃H₆的t₅₀降到170℃,CO的t₅₀降到了150℃,显示了良好的Pt、Pd协同效应;H₂-TPR表征和抗硫性结果分析表明,高比例Pt/Pd催化剂具有更多的表面活性氧,其相对数值与催化剂抗硫性能的关联度高,在催化剂硫酸盐中毒的条件下,更有利于催化反应的进行。     

离子液体中水热合成Pt-Pd/MWCNTs和Pd/MWCNTs催化剂

采用水热合成法, 以离子液体1-乙基-3-甲基咪唑四氟硼酸盐(C₆H₁₁BF₄N₂, EMIBF₄)为溶剂制备了Pt-Pd/MWCNTs(Multi-walled carbon nanotubes)和Pd/MWCNTs催化剂. X射线衍射(XRD)和X射线能量散射谱(EDS)测试证明了Pt-Pd合金和Pd纳米颗粒在MWCNTs的表面生成. 透射电子显微镜(TEM)照片不仅证明了在MWCNTs表面Pt-Pd, Pd纳米颗粒的生成, 而且还表明样品颗粒的平均粒径约为4 nm. 循环伏安(CV)和交流阻抗(EIS)测试表明, 在碱性环境下, 乙醇在Pt-Pd/MWCNTs和Pd/MWCNTs修饰的玻碳(GC)电极上均能发生氧化反应, 与Pd/MWCNTs修饰的电极相比, 在Pt-Pd/MWCNTs上乙醇的起峰电位负移了大约200 mV, 且具有更高的氧化峰电流值.     

Electrochemical Synthesis of Tetrahexahedral Rhodium Nanocrystals with Extraordinarily High Surface Energy and High Electrocatalytic Activity

Noble metal nanocrystals (NCs) enclosed with high‐index facets hold a high catalytic activity thanks to the high density of low‐coordinated step atoms that they exposed on their surface. Shape‐control synthesis of the metal NCs with high‐index facets presents a big challenge owing to the high surface energy of the NCs, and the shape control for metal Rh is even more difficult because of its extraordinarily high surface energy in comparison with Pt, Pd, and Au. The successful synthesis is presented of tetrahexahedral Rh NCs (THH Rh NCs) enclosed by {830} high‐index facets through the dynamic oxygen adsorption/desorption mediated by square‐wave potential. The results demonstrate that the THH Rh NCs exhibit greatly enhanced catalytic activity over commercial Rh black catalyst for the electrooxidation of ethanol and CO.     

Formation of a Highly Reactive Cobalt Nanocluster Crystal within a Highly Negatively Charged Porous Coordination Cage

Earth‐abundant first‐row transition‐metal nanoclusters (NCs) have been extensively investigated as catalysts. However, their catalytic activity is relatively low compared with noble metal NCs. Enhanced catalytic activity of cobalt NCs can be achieved by encapsulating Co NCs in soluble porous coordination cages (PCCs). Two cages, PCC‐2a and 2b, possess almost identical cavity in shape and size, while PCC‐2a has five times more net charges than PCC‐2b. Co²⁺ cations were accumulated in PCC‐2a and reduced to ultra‐small Co NCs in situ, while for PCC‐2b, only bulky Co particles were formed. As a result, Co NCs@PCC‐2a accomplished the highest catalytic activity in the hydrolysis of ammonium borane among all the first‐row transition‐metals NCs. Based on these results, it is envisioned that confining in the charged porous coordination cage could be a novel route for the synthesis of ultra‐small NCs with extraordinary properties.