One‐Pot Synthesis of Carbon‐Supported Dendritic Pd‐Au Nanoalloys for Electrocatalytic Ethanol Oxidation

One‐pot synthesis of carbon‐supported Pd‐Au alloy nanoparticles with well‐defined dendritic shape (Pd‐Au_den/C) was achieved by co‐reduction of K₂PdCl₄/HAuCl₄ mixtures in a molar ratio of 1:1 with hydrazine in the presence of Vulcan XC‐72R. The prepared Pd‐Au_den/C exhibited significantly enhanced performance in the electrocatalytic oxidation of ethanol compared with dendritic Pd nanoparticles and a commercial Pd/C catalyst. Pd‐Au_den/C even showed higher durability in electro‐oxidation of ethanol than the supported catalyst prepared by the deposition of presynthesized dendritic Pd‐Au nanoparticles on the carbon support. The experimental results clearly indicate that enhanced interaction between nanoparticle catalysts and carbon support through the one‐pot synthesis protocol can improve the durability of the electrocatalysts.     

Long‐Lasting Oscillations in the Electro‐Oxidation of Formic Acid on PtSn Intermetallic Surfaces

Even when in contact with virtually infinite reservoirs, natural and manmade oscillators typically drift in phase space on a time‐scale considerably slower than that of the intrinsic oscillator. A ubiquitous example is the inexorable aging process experienced by all living systems. Typical electrocatalytic reactions under oscillatory conditions oscillate for only a few dozen stable cycles due to slow surface poisoning that ultimately results in destruction of the limit cycle. We report the observation of unprecedented long‐lasting temporal oscillations in the electro‐oxidation of formic acid on an ordered intermetallic PtSn phase. The introduction of Sn substantially increases the catalytic activity and retards the irreversible surface oxidation, which results in the stabilization of more than 2200 oscillatory cycles in about 40 h; a 30–40‐fold stabilization with respect to the behavior of pure Pt surfaces. The dynamics were modeled and numerical simulations point to the surface processes underlying the high stability.     

High‐Efficiency Encapsulation of Pt Nanoparticles into the Channel of Carbon Nanotubes as an Enhanced Electrocatalyst for Methanol Oxidation

Pt‐based nanostructures serving as anode catalysts for the methanol oxidation reaction (MOR) have been widely studied for many years. Nevertheless, challenging issues such as poor reaction kinetics and the short‐term stability of the MOR are the main drawbacks of such catalysts and limit their applications. Herein, we have developed a facile approach to encapsulate Pt nanoparticles (NPs) inside the nanochannels of porous carbon nanotubes (CNTs; Pt‐in‐CNTs) as a new enhanced electrocatalytic material. The as‐prepared CNTs offer simultaneously ordered diffusion channels for ions and a confinement effect for the NPs, which both facilitate the promotion of catalytic kinetics and avoid the Ostwald ripening of Pt NPs, thus leading to high activity and durable cycle life as an anode catalyst for MOR. This work provides a new approach for enhancing the stability and activity by optimizing the structure of the catalyst, and the Pt‐in‐CNTs represent the most durable catalysts ever reported for MOR.     

制备方法对直接乙醇燃料电池阳极PtSn/C催化剂性能的影响

 对比研究了用三种液相沉积还原法制备的PtSn/C催化剂,并用X射线衍射、透射电镜和程序升温还原等技术表征了催化剂的形貌、结构及组成. 用乙二醇还原法制备的PtSn/C(EG)催化剂的平均粒径最小(约为1.8 nm), 且分布均匀, Sn以多种价态存在于PtSn/C(EG)中. 采用循环伏安法和直接乙醇燃料电池单池评价了三种PtSn/C催化剂对乙醇氧化反应的催化活性,探索了单池性能与催化剂粒径及组成的关系. 结果表明, PtSn/C(EG)催化剂具有较高的催化乙醇氧化活性. 这可能是因为PtSn/C(EG)催化剂的金属粒径较小, Pt晶格发生了适当的扩张以及SnO2能够在较低电位下提供含氧物种的缘故.     

Size‐Controllable Synthesis of Trimetallic RhPdPt Island‐Shaped Nanoalloys with Enhanced Electrocatalytic Performance for Ethanol Oxidation in Alkaline Medium

Size‐controllable, high‐yield, island‐shaped RhPdPt trimetallic nanocrystals with sub‐2.0 nm islands have been successfully synthesized through a facile aqueous solution approach. The results of X‐ray diffraction (XRD), energy‐dispersive X‐ray (EDX) line scanning and elemental mapping analysis showed the as‐synthesized RhPdPt nanocrystals are alloy structures. These island‐shaped RhPdPt trimetallic nanoalloys showed a composition‐dependent electrocatalytic performance for ethanol oxidation in alkaline medium. Due to the special structure and intermetallic synergies, the Rh₁₀Pd₄₀Pt₅₀ nanoalloys exhibited an enhanced catalytic activity and durability relative to island‐shaped Pd₅₀Pt₅₀ bimetallic nanoalloys and commercial Pt black. The peak current density for Rh₁₀Pd₄₀Pt₅₀ nanoalloys was 1.81 and 1.38 times that for commercial Pt black and Pd₅₀Pt₅₀ nanoalloys, respectively. In addition, the peak potential on Rh₁₀Pd₄₀Pt₅₀ nanoalloys decreased 42 mV relative to commercial Pt black and Pd₅₀Pt₅₀ nanoalloys.     

Surfactant-Free Synthesis of Three-Dimensional Perovskite Titania-Based Micron-Scale Motifs Used as Catalytic Supports for the Methanol Oxidation Reaction

We synthesized and subsequently rationalized the formation of a series of 3D hierarchical metal oxide spherical motifs. Specifically, we varied the chemical composition within a family of ATiO₃ (wherein “A” = Ca, Sr, and Ba) perovskites, using a two-step, surfactant-free synthesis procedure to generate structures with average diameters of ~3 microns. In terms of demonstrating the practicality of these perovskite materials, we have explored their use as supports for the methanol oxidation reaction (MOR) as a function of their size, morphology, and chemical composition. The MOR activity of our target systems was found to increase with decreasing ionic radius of the “A” site cation, in order of Pt/CaTiO₃ (CTO) > Pt/SrTiO₃ (STO) > Pt/BaTiO₃ (BTO). With respect to morphology, we observed an MOR enhancement of our 3D spherical motifs, as compared with either ultra-small or cubic control samples. Moreover, the Pt/CTO sample yielded not only improved mass and specific activity values but also a greater stability and durability, as compared with both commercial TiO₂ nanoparticle standards and precursor TiO₂ templates.     

Chitosan‐Functionalized Carbon Nanotubes as Support for the High Dispersion of PtRu Nanoparticles and their Electrocatalytic Oxidation of Methanol

Carbon nanotubes (CNTs) were non‐covalently functionalized with chitosan (Chit) and then employed as the support for PtRu nanoparticles. The functionalization was carried out at room temperature without the use of corrosive acids, thereby preserving the integrity and the electronic conductivity of the CNTs. Transmission electron microscopy reveals that PtRu nanoparticles were highly dispersed on the surface of Chit‐functionalized CNTs (CNT‐Chit) with small particle‐size. Cyclic voltammetry studies indicated that the PtRu nanoparticle/CNT‐Chit nanohybrids have a higher electrochemical surface area, electrocatalytic performance, and stability towards methanol oxidation compared to PtRu nanoparticles supported on the pristine CNTs.     

Controlled Synthesis and Enhanced Catalytic and Gas‐Sensing Properties of Tin Dioxide Nanoparticles with Exposed High‐Energy Facets

A morphology evolution of SnO₂ nanoparticles from low‐energy facets (i.e., {101} and {110}) to high‐energy facets (i.e., {111}) was achieved in a basic environment. In the proposed synthetic method, octahedral SnO₂ nanoparticles enclosed by high‐energy {111} facets were successfully synthesized for the first time, and tetramethylammonium hydroxide was found to be crucial for the control of exposed facets. Furthermore, our experiments demonstrated that the SnO₂ nanoparticles with exposed high‐energy facets, such as {221} or {111}, exhibited enhanced catalytic activity for the oxidation of CO and enhanced gas‐sensing properties due to their high chemical activity, which results from unsaturated coordination of surface atoms, superior to that of low‐energy facets. These results effectively demonstrate the significance of research into improving the physical and chemical properties of materials by tailoring exposed facets of nanomaterials.     

Size‐Dependent Electrocatalytic Activity of Free Gold Nanoparticles for the Glucose Oxidation Reaction

Understanding the fundamental relationship between the size and the structure of electrode materials is essential to design catalysts and enhance their activity. Therefore, spherical gold nanoparticles (GNSs) with a mean diameter from 4 to 15 nm were synthesized. UV/Vis spectroscopy, transmission electron microscopy, and under‐potential deposition of lead (UPD_Pb) were used to determine the morphology, size, and surface crystallographic structure of the GNSs. The UPD_Pb revealed that their crystallographic facets are affected by their size and the growth process. The catalytic properties of these GNSs toward glucose electrooxidation were studied by cyclic voltammetry, taking into account the scan rate and temperature effects. The results clearly show the size‐dependent electrocatalytic activity for glucose oxidation reactions that are controlled by diffusion. Small GNSs with an average size of 4.2 nm exhibited high catalytic activity. This drastic increase in activity results from the high specific area and reactivity of the surface electrons induced by their small size. The reaction mechanism was investigated by in situ Fourier transform infrared reflectance spectroscopy. Gluconolactone and gluconate were identified as the intermediate and the final reaction product, respectively, of the glucose electrooxidation.     

Palladium–Cobalt Nanotube Arrays Supported on Carbon Fiber Cloth as High‐Performance Flexible Electrocatalysts for Ethanol Oxidation

PdCo nanotube arrays (NTAs) supported on carbon fiber cloth (CFC) (PdCo NTAs/CFC) are presented as high‐performance flexible electrocatalysts for ethanol oxidation. The fabricated flexible PdCo NTAs/CFC exhibits significantly improved electrocatalytic activity and durability compared with Pd NTAs/CFC and commercial Pd/C catalysts. Most importantly, the PdCo NTAs/CFC shows excellent flexibility and the high electrocatalytic performance remains almost constant under the different distorted states, such as normal, bending, and twisting states. This work shows the first example of Pd‐based alloy NTAs supported on CFC as high‐performance flexible electrocatalysts for ethanol oxidation.     

Mild Synthesis of Pt/SnO2/Graphene Nanocomposites with Remarkably Enhanced Ethanol Electro‐oxidation Activity and Durability

We have designed a new Pt/SnO₂/graphene nanomaterial by using L ‐arginine as a linker; this material shows the unique Pt‐around‐SnO₂ structure. The Sn²⁺ cations reduce graphene oxide (GO), leading to the in situ formation of SnO₂/graphene hybrids. L ‐Arginine is used as a linker and protector to induce the in situ growth of Pt nanoparticles (NPs) connected with SnO₂ NPs and impede the agglomeration of Pt NPs. The obtained Pt/SnO₂/graphene composites exhibit superior electrocatalytic activity and stability for the ethanol oxidation reaction as compared with the commercial Pt/C catalyst owing to the close‐connected structure between the Pt NPs and SnO₂ NPs. This work should have a great impact on the rational design of future metal–metal oxide nanostructures with high catalytic activity and stability for fuel cell systems.     

Chemico‐Physical Synthesis of Surfactant‐ and Ligand‐Free Gold Nanoparticles and Their Anti‐Galvanic Reduction Property

Galvanic reduction (GR) is a classic reaction. In simple terms, metals can reduce less reactive (or more noble) metal ions, while the opposite—metals reduce more reactive (or less noble) metal ions—should not occur. However, recently we found that anti‐galvanic reduction (AGR) occurred to thiolated gold and silver nanoparticles. However, the essential issue whether the occurrence of AGR requires the assistance of reductive thiolate ligands or not still remained unanswered. In this work, by using a novel protocol (chemical reduction and physical ablation), we synthesized surfactant‐ and ligand‐free gold nanoparticles. We found that these as‐prepared nanoparticles can reduce silver ions and copper ions, thus illustrating that AGR is not dependent on reductive ligands. Further experiments demonstrated that AGR is applicable to other metal (such as Pt and Pd) nanoparticles and that the AGR process is size‐dependent. Finally, it was found that the Raman scattering signals of Rhodamine 6G are distinctly enhanced on the gold nanoparticles that had been reacted with silver ions, which indicates the use of AGR for tuning the property of nanoparticles.     

Synergistic Effect between Metal–Nitrogen–Carbon Sheets and NiO Nanoparticles for Enhanced Electrochemical Water‐Oxidation Performance

Identifying effective means to improve the electrochemical performance of oxygen‐evolution catalysts represents a significant challenge in several emerging renewable energy technologies. Herein, we consider metal–nitrogen–carbon sheets which are commonly used for catalyzing the oxygen‐reduction reaction (ORR), as the support to load NiO nanoparticles for the oxygen‐evolution reaction (OER). FeNC sheets, as the advanced supports, synergistically promote the NiO nanocatalysts to exhibit superior performance in alkaline media, which is confirmed by experimental observations and density functional theory (DFT) calculations. Our findings show the advantages in considering the support effect for designing highly active, durable, and cost‐effective OER electrocatalysts.     

Functionalization of Carbon Nanotubes by an Ionic‐Liquid Polymer: Dispersion of Pt and PtRu Nanoparticles on Carbon Nanotubes and Their Electrocatalytic Oxidation of Methanol

Small beginnings : Metal nanoparticle/CNT nanohybrids are synthesized from carbon nanotubes (CNTs) functionalized with an ionic‐liquid polymer. The Pt and PtRu nanoparticles with narrow size distribution (average diameter: (1.3±0.4) nm for PtRu, (1.9±0.5) nm for Pt) are dispersed uniformly on the CNTs (see images) and show good performance in methanol electrooxidation.

     

Synthesis of Platinum and Tin Oxide Co‐functionalized Single‐walled Carbon Nanotubes (Pt/SnO2/SWNTs) and their Sensing Properties toward Carbon Monoxide

Pt and SnO₂ were co‐functionalized on single‐walled carbon nanotubes (SWNTs) assembled on microelectrodes by electrochemical deposition where Pt nanoparticle's morphology, size, and density were tuned by controlling the applied potential and time. The systematic study to obtain the optimum condition for Pt‐decorated SnO₂/SWNTs (Pt/SnO₂/SWNTs) were performed and also correlate with its CO sensing performance. Illumination‐dependent sensing performance was examined using red, green and UV LED as light sources at room temperature. Under UV illumination, the sensitivity of Pt/SnO₂/SWNTs was enhanced to 2.1 %/ppm_V of CO with the lower detection limit of 0.05 ppm_V.