Electrospinning Ru doped Co3O4 porous nanofibers as promising bifunctional catalysts for oxygen evolution and oxygen reduction reactions

Enhancing the catalytic activity for oxygen evolution and oxygen reduction reactions is critical for rechargeable metal-air batteries. Herein, coral-like Ru-doped cobalt oxide nanofibers are prepared by electrospinning and subsequent heat treatment, which reduce the charge transfer resistance of cobalt oxide and optimize its active sites. Moreover, the large specific surface area and rich porosity of the one-dimensional nanomaterials prepared by the electrospinning method markedly improved the catalytic activity. Under the same catalyst load, Ru-doped cobalt oxide nanofibers have an overpotential of 300 mV, which is smaller than that of ruthenium oxide. In the oxygen reduction reaction, the positive half-wave potential of Ru-doped cobalt oxide nanofibers and Pt/C is the same (0.81 V). This work combines the strategies of doping and the advantages of electrospinning nanofibers to make a breakthrough in the catalytic activity of doped cobalt oxide nanofibers, and provides a new basis for the design of one-dimensional nanofiber bifunctional catalysts.     

Pt-rich shell coated Ni nanoparticles as catalysts for methanol electro-oxidation in alkaline media

The Pt-rich shell coated Ni nanoparticles in size of 8.9–12.1 nm were synthesized by chemical deposition via successive reduction of NiCl₂ and H₂PtCl₆, respectively, in an ethylene glycol solution and characterized by TEM, XPS, ICP–AES, and XRD techniques. The electrochemical evaluation showed that as-prepared core–shell structural nanoparticles, as a catalyst for methanol electro-oxidation in alkaline media, not only exhibited better catalytic activity and resistance to carbonaceous intermediate poison than pure solid Pt nanoparticles but also decreased wastage of expensive Pt.     

Pd-Ni nanoparticles supported on titanium oxide as effective catalysts for Suzuki-Miyaura coupling reactions

We have successfully prepared a series of Pd-Ni/TiO₂ catalysts by a one-step impregnation-reduction method. Among these catalysts with different compositions of Ni and Pd, the one with the Ni:Pd ratio of 2.95 showed the best activity. Small monodispersed Pd-Ni bimetallic nanoparticles were loaded on the surface of titanium oxide nanopowder as confirmed with TEM and EDS mapping. The XPS analysis demonstrated that Pd exists as 31% Pd(II) species and 69% Pd(0) species and all nickel is Ni(II). The prepared Pd-Ni/TiO₂ exhibited enhanced catalytic activity compared to an equal amount of Pd/TiO₂ for Suzuki-Miyaura reactions together with excellent applicability and reusability.

Open image in new window

     

Heterostructures of MXenes and CoNx-Graphene as highly active electrocatalysts for hydrogen evolution reaction in alkaline media

Journal of Applied Electrochemistry - Hydrogen evolution reaction (HER) plays a vital role in renewable energy conversion for the development of hydrogen-based energy sources. Lately,...     

The effect of electrodeposition potential on catalytic properties of Ni nanoparticles for hydrogen evolution reaction (HER) in alkaline media

Journal of Applied Electrochemistry - The fabrication of non-precious electrocatalyst for water splitting has a great potential. So, Ni electrocatalysts are considered one of the most auspicious...     

Preparation and investigation of Pd doped Cu catalysts for selective hydrogenation of acetylene

A series of PdCu bimetallic catalysts with low Cu and Pd loadings and different Cu: Pd atomic ratios were prepared by conventionally sequential impregnation (CSI) and modified sequential impregnation (MSI) of Cu and Pd for selective hydrogenation of acetylene. Characterization indicates that the supported copper (II) nitrate in the PdCu bimetallic catalysts prepared by MSI can be directly reduced to Cu metal particles due to the hydrogen spillover from Pd to Cu(NO₃)₂ crystals. In addition, for the catalysts prepared by MSI, Pd atoms can form PdCu alloy on the surface of metal particles, however, for the catalysts prepared by CSI, Pd tends to migrate and exist below the surface layer of Cu. Reaction results indicate that compared with CSI, the MSI method enables samples to possess preferable stability as well as comparable reaction activity. This should be due to the MSI method in favor of the formation of PdCu alloy on the surface of metal particles. Moreover, even Pd loading is super low, <0.045 wt-% in this study, by through adjusting Cu loading to an appropriate value, attractive reactivity and selectivity still can be achieved.     

Methanol oxidation on gold nanoparticles in alkaline media: Unusual electrocatalytic activity

Methanol oxidation on gold nanoparticles has been studied using cyclic voltammetry in alkaline media. The onset for methanol oxidation in 0.1 M NaOH solutions is at ca. 0.3 V (RHE) and the currents reach a maximum value at 0.8 V. In 1 M NaOH solutions, oxidation currents are measured at potentials as low as 0.1 V. Although the currents are significantly smaller than the expected limiting diffusion current for methanol oxidation, oxidation currents are partially controlled by diffusion, as revealed by rotating disk experiments. This suggests that only a small fraction of the nanoparticles is active for the oxidation. It is proposed that formate is the final product of the oxidation and formaldehyde is an active intermediate in the process.     

A nickel molybdenite cathode for the hydrogen evolution reaction in alkaline media

The characteristics and mechanism of the hydrogen evolution reaction on a nickel sulphide electrode incorporating molybdenite particles are described. At 25°C the overpotential for the reaction is 300 mV lower than that of the mild steel cathodes used in unipolar electrolysers. The material shows good stability under long term operation.     

Depolarization of the hydrogen evolution reaction on cadmium electrodes in alkaline media

Depolarization of the hydrogen evolution reaction on high purity polycrystalline cadmium electrodes in alkaline media (12pH14 and 5T55°C) produced by cathodization in the range of potential comprised between the Cd/Cd(OH)₂ electrode potential and the net HER potential under solution stirring conditions has been studied. The depolarization effect depends on the perturbing potential programme and it is little affected by the alkaline cation in solution. Results are discussed in terms of three concurrent reactions, namely the electrochemical formation of Cd(OH)₂ and soluble Cd(OH) ₃ ^– , the HER and the electrocrystallization of cadmium renewing the fresh active sites for the HER, SEM micrographs of activated cadmium electrodes reveal a heterogeneous surface topography of the new cadmium layers.     

生物质焦油衍生氮掺杂多孔碳负载Co3O4纳米晶的制备及双功能氧反应催化

以生物质焦油活化多级孔碳为骨架,通过一步水热合成同时实现氮掺杂和Co₃O₄纳米粒子负载,获得Co₃O₄@N/C复合催化剂。对比研究结果表明,凭借复合材料中活性Co₃O₄和N掺杂结构之间的协同效应,Co₃O₄@N/C复合催化剂对氧还原（ORR）和析氧反应（OER）均表现出较高的催化活性,ORR和OER启动电位电势差ΔE为0.99V;其中,ORR极限扩散电流密度为-5.10mA/cm²,与贵金属Pt/C相当。此外,Co₃O₄@N/C具有优异的氧还原稳定性,在经3000次循环伏安法扫描后,Co₃O₄@N/C的极限扩散电流密度仍能保持89.9%。这一生物质焦油衍生碳所构筑的N掺杂多孔碳负载Co₃O₄纳米晶复合材料在燃料电池和金属空气电池等领域具有巨大的应用潜力。     

Development of novel Lewis acid catalysts for selective organic reactions in aqueous media

New types of Lewis acids as water-compatible catalysts have been developed. Various metal salts were found to work as Lewis acid catalysts in aqueous media, and catalytic asymmetric aldol reactions in such media have been attained. Furthermore, Lewis acid-surfactant combined catalysts, which can be used for reactions in water without using any organic cosolvents, have been also developed. These investigations will contribute to reducing the use of harmful organic solvents and to develop efficient catalytic systems which cannot be realized in conventional organic solvents.     

A highly active Pd coated Ag electrocatalyst for oxygen reduction reactions in alkaline media

We synthesized and characterized a highly active electrocatalyst for oxygen reduction reactions (ORRs) in alkaline media by coating carbon-supported silver nanoparticles with Pd (Pd@Ag/C) via a galvanic displacement method. The electrochemical measurements were carried out using an ultrathin film rotating disk electrode. Compared to the Pt/C electrocatalyst, the specific and mass activities of the Pd@Ag/C were enhanced by a factor of 3 and 2.5, respectively. The potentiostatic measurements showed that the Pd@Ag/C is less stable than the Pt/C at the potential of −0.1 V vs. Hg/HgO/OH⁻ in alkaline media. The Pd@Ag/C is insensitive to alcohol, and, as a cathode electrocatalyst of a direct alcohol fuel cell, can resist poisoning by the possible alcohol crossover from the anode.     

Comparison of immobilized Box and azaBox–Cu(II) complexes as catalysts for enantioselective Mukaiyama aldol reactions

Enantioselective Mukaiyama aldol reactions of different α-ketoesters was tested with copper complexes of chiral Box and azaBox ligands in both homogeneous and heterogeneous systems. Results in the homogeneous reactions were greatly influenced by the nature of the ketoester, the chiral ligand, and the reaction solvent. In the case of supported catalysts, the use of strongly coordinating azaBox ligands prevented the leaching of metal but reduced the Lewis acidity, and thus the catalytic activity, and did not solve the problem of poisoning by strong coordination of products, byproducts, or solvents. The counter-ion effect also was very significant, and electrostatic immobilization was efficient only with Box ligands (up to 86% ee at room temperature), whereas covalent immobilization allowed the use of azaBox ligands (up to 85% ee at room temperature) in the heterogeneous phase. Recovered deactivated solids could be reused in a reaction with a completely different mechanism that does not require acid centers, such as cyclopropanation.     

凹凸棒土固载N-杂环卡宾催化安息香缩合反应

本文将五种不同的NHCs催化剂前体接枝到凹凸棒土表面，制备了五种负载型NHCs催化剂。通过FT-IR、元素分析、BET和SEM对五种催化剂进行了表征，表征结果表明NHCs催化剂前体成功地固定在凹凸棒土表面。进一步的实验结果表明，这些负载型NHC可以作为安息香反应的有效催化剂。接着探究了这些负载型催化剂催化安息香反应的优化条件。结果发现，当BTBCl@ATP(催化剂B, 1 mmol%咪唑盐)作为催化剂，0.4当量NaOH作为碱，2ml CH3OH作为溶剂，在110℃油浴中，在Ar气氛中反应8小时，收率最高。在此优化条件下，负载型NHCs催化剂可以催化多种芳香醛的安息香反应，产率为61-86%。催化剂的重复使用实验表明，这些负载型催化剂可以简单地从反应体系中分离出来，重复使用四次后，这些负载型催化剂的催化活性没有明显下降。     

3D Network nanostructured NiCoP nanosheets supported on N-doped carbon coated Ni foam as a highly active bifunctional electrocatalyst for hydrogen and oxygen evolution reactions

A highly active bi-functional electrocatalyst towards both hydrogen and oxygen evolution reactions is critical for the water splitting. Herein, a self-supported electrode composed of 3D network nanostructured NiCoP nanosheets grown on N-doped carbon coated Ni foam (NiCoP/NF@NC) has been synthesized by a hydrothermal route and a subsequent phosphorization process. As a bifunctional electrocatalyst, the NiCoP/NF@NC electrode needs overpotentials of 31.8 mV for hydrogen evolution reaction and 308.2 mV for oxygen evolution reaction to achieve the current density of 10 mA·cm⁻² in 1 mol·L⁻¹ KOH electrolyte. This is much better than the corresponding monometal catalysts of CoP/NF@NC and NiP/NF@NC owing to the synergistic effect. NiCoP/NF@NC also exhibits low Tafel slope, and excellent long-term stability, which are comparable to the commercial noble catalysts of Pt/C and RuO₂.     

Agglomerates and granules of nanoparticles as filter media for submicron particles

An experimental study on filtration of submicron solid and liquid aerosol particles by using a filter media composed of agglomerates or granules of nanoparticles is described. Fumed silica nanoagglomerates, carbon black granules, silica shells, activated carbon granules, glass beads and nanoporous hydrophobic aerogel were among the granular filter media tested and compared to a commercially available HEPA fiber-based filter. Other than the glass beads which were used for comparison purposes, the primary particle size of the agglomerates/granules is of nanometer scale, but they agglomerate to form porous structures of about several hundreds of microns which were customized as packed (deep bed) or fluidized bed filters and challenged against submicron solid and liquid aerosols. For packed bed filters, the size of the granules has been optimized to a range of 150-500 µm with a filter thickness of about 1-3 in. and superficial gas velocities of less than 4 cm/s. Fluidized beds required granules smaller than 150 µm and the height of the bed was in the range of 15-40 cm.The customized filters and a HEPA fiber-based filter were challenged simultaneously against the same aerosol at the same superficial gas velocities. When using carbon black or aerogel granules as filter media, collection efficiencies comparable or even higher than HEPA fiber-based filters are obtained, but with the advantage of extra filtration capacity due to the deep bed configuration and the absorption of liquids into the porosity of the media. A fluidized bed filter of aerogel granules not only provides higher collection efficiency and larger capacity than a HEPA fiber-based filter when challenged against both oil mist and solid aerosols but also has an extremely low pressure drop compared to a packed bed filter and can be operated continuously with respect to removing saturated granules and adding fresh ones.     

Metal-organic framework-derived Ni doped Co3S4 hierarchical nanosheets as a monolithic electrocatalyst for highly efficient hydrogen evolution reaction in alkaline solution

Hierarchical nanostructure construction and electronic structure engineering are commonly employed to increase the electrocatalytic activity of HER electrocatalysts. Herein, Ni doped Co₃S₄ hierarchical nanosheets on Ti mesh (Ni doped Co₃S₄ HNS/TM) were successfully prepared by using metal organic framework (MOF) as precursor which was synthesized under ambient condition. Characterization results confirmed this structure and Ni incorporation into Co₃S₄ lattice as well as the modified electronic structure of Co₃S₄ by Ni doping. Alkaline HER performance showed that Ni doped Co₃S₄ HNS/TM presented outstanding HER activity with 173 mV overpotential at -10 mA·cm^-2, surpassing most of metal sulfide-based electrocatalysts. The hierarchical structure, superior electrical conductivity and electronic structure modulation contributed to the accelerated water dissociation and enhanced intrinsic activity. This work provides a new avenue for synthesizing hierarchical nanostructure and simultaneously tuning the electronic structure to promote HER performance, which has potential application in designing highly efficient and cost-effective HER nanostructured electrocatalyst.