Electrosynthesis of eco-friendly electrocatalyst based nickel-copper bimetallic nanoparticles supported on poly-phenylenediamine with highest current density and early ethanol oxidation onset potential

Bimetallic catalysts have been investigated as the most efficient materials to accelerate the chemical transformations at the anode in Direct Ethanol Fuel Cells. A comparative study is presented here to synthesize Ni–Cu bimetallic nanoparticles for the ethanol oxidation reaction on three conducting polymers: poly-ortho-phenylenediamine, poly-meta-phenylenediamine, and poly-para-phenylenediamine. X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and Electrochemical Impedance Spectroscopy (EIS) were used to analyze the modified electrodes. A series of bimetallic Ni–Cu nanoparticles with tunable ratios were successfully synthesized by simply changing the concentrations of Nickel and Copper. It has been confirmed that the best Ni/Cu molar ratio was 25% in the aspect of catalytic performance. The electrocatalyst exhibited an excellent catalytic activity with an anodic current of 70.5 mA cm^?2 at the lowest onset potential of 0.39 V with impressive stability. Ni₄Cu₁/PpPD should be considered as a good alternative to noble metal anode catalyst.     

Formation of single-crystalline BaTiO3 nanorods from glycolate by tuning the supersaturation conditions

We have studied peculiarities in the formation of single-crystalline barium titanate (BaTiO₃) nanorods from a glycolate-mediated complex via a single-step hydrothermal process under different supersaturation (S_R) conditions. X-ray diffraction (XRD) showed the formation of pure BaTiO₃ with an S_R of above 19. The tetragonality for the BaTiO₃ (c/a) reached 1.013 at S_R = 19–29 and dropped to 1.010 for S_R = 39. According to the transmission electron microscopy (TEM) and XRD analyses, the rod-shaped particles exhibited single crystallinity and crystal growth along the [001] plane. With scanning electron microscopy (SEM), the morphological evolution from a plate-shaped intermediate precursor (S_R = 6–9) to a rod-shaped product with an aspect ratio of 6–9 (S_R = 19–29), and to non-polar material with an irregular structure (S_R = 39), was observed. The negative slope, linear dependence of the particles’ width and length on the supersaturation level in the range S_R = 19–39 was established for the first time. The replacement of the prevailing crystallization mechanism from in-situ topotactic transformation into dissolution-precipitation above S_R = 19 was observed. It was shown that with a simple regulation of the S_R, the structural and morphological characteristics of the obtained BaTiO₃ nanoparticle can be effectively tuned.     

磁性硅铁载铜吸附Hg0动力学机制及密度泛函研究

采用粉末冶金法将纳米单质铜(Cu⁰)、硅铁(FeSi)、四氧化三铁硅涂层(Fe₃O₄@SiO₂)混合煅烧并制备出新型磁性硅铁载铜吸附剂MagFeSi-Cu⁰。实验研究不同烟气温度下MagFeSi-Cu⁰的汞吸附能力基础上,结合颗粒内扩散模型、准二阶动力学模型、Elovich模型及Bangham模型分析了MagFeSi-Cu⁰吸附Hg⁰过程的主要控制步骤。在此基础上,依据密度泛函理论(DFT)研究了不同反应温度下FeSi表面Cu⁰原子与Hg⁰原子的汞齐作用机制。研究结果表明,Bangham模型的拟合值与MagFeSi-Cu⁰汞吸附实验值拟合度最高,MagFeSi-Cu⁰表面痕量Hg⁰吸附由汞的外扩散和表面铜汞齐吸附共同控制;通过密度泛函计算,发现Cu⁰颗粒表面Cu-Hg齐吸附能为-0.534 eV,当烟气温度从80℃上升至200℃时,Hg⁰原子与单质Cu原子的吸附自由能从-22.47 kJ/mol下降至-13.96 kJ/mol,这些结果为深入了解Hg⁰在Cu(111)表面的反应机理提供了理论基础。     

Facile synthesis of asymmetric patchy Janus Ag/Cu particles and study of their antifungal activity

Asymmetric patchy Ag/Cu Janus nanoparticles (NPs) were synthesized via a “seed-mediated” approach. This is the first report of synthesis of nanometer sized metal-based Janus NPs without using complicated methods. Selective adsorption of the surfactant onto the seed NPs leads to the formation of Janus type structure. Subsequently the reduction potential of Ag⁺/Ag⁰ and Cu²⁺/Cu⁰ systems directs the formation of the “patch”. The patchy Janus NPs show significant antifungal activity towards a potent rice pathogen thus offering the prospect of future application in crop protection.     

Mesoporous electroactive silver doped calcium borosilicates: Structural,antibacterial and myogenic potential relationship of improved bio-ceramics

In this work improved electroactive mesoporous Ag-doped bio-ceramics for medical usages are developed, examining their structural, electrical, in-vitro bioactivity, cell cultures and antibacterial properties against various classical pathogenic bacteria. Ag-containing mesoporous bio-ceramics (MBCs): xmol%Ag₂O - (100-x)[45.8CaO-8.4B₂O₃-45.8SiO₂] where x = 2, 5, 7.5 and 10 were synthesized through a sol-gel method. The small angle X-ray scattering and electron microscopy studies reveal the embedment of silver nanoparticles in the samples. Existence of silver as Ag⁺/Ag⁰ forms in the samples is confirmed by X-ray photoelectron spectroscopy. The N₂ adsorption-desorption analysis evidence the mesoporous structure of the samples. The electrical conductivity of samples increases from 5.4 x 10^?8 S cm^?1 for x = 2 to 1.9 x 10^?6 S cm^?1 for x = 7.5 and then decreases to 0.9 x 10^?6 S cm^?1 for x = 10 at 110 °C. In vitro bioactivity studies revealed that Ag-containing MBCs hold the bone-like hydroxyapatite formation after immersion in human blood plasma like-solution such as Dulbecco's Modi?ed Eagle's Medium. The antibacterial effect of samples against pathogenic bacteria (S. aureus, E. coli, P. monas aeruginosa, and B. cereus) increases with Ag concentration (x = 7.5) and then decreases with Ag content (x = 10). Antibacterial effect is greater for the sample with high electrical conductivity. The cell culture studies evidence not considerable cytotoxic effects for Ag-containing MBCs. Finally, the C2C12 myoblast cell culture studies reveal the significant cell growths and differentiation (myogenesis) for high electrical conducting Ag-containing MBCs.     

Enhancement effect of zero-valent iron nanoparticle and iron oxide nanoparticles on dark fermentative hydrogen production from molasses-based distillery wastewater

This study investigates the effect of two different iron compounds (zero-valent iron nanoparticle: nZVI and iron oxide nanoparticles: nIO) and pH on fermentative biohydrogen production from molasses-based distillery wastewater. The nZVI and nIO of optimum particle sizes of 50 nm and 55 nm respectively were synthesized and applied for fermentative hydrogen (H₂) production. The addition of nIO & nZVI at (0.7 g/L, pH: 6) resulted in the highest H₂ yield, H₂ production rate, H₂ content and COD reduction. Moreover, the kinetic parameters of H₂ production potential (P) and H₂ production rate (R_m) increased to 387 mL, and 22.2 mL/h, respectively for nZVI, these values were 363 mL and 21.8 mL/h for nIO. The results obtained indicated the positive effect of nZVI and nIO addition on enhanced fermentative H₂ production. The addition of nZVI & nIO resulted in 71% and 69.4% enhancement in biohydrogen production respectively.     

Mechanochemically assisted fabrication of ultrafine Pd nanoparticles on natural waste-derived nitrogen-doped porous carbon for the efficient formic acid decomposition

Utilizing natural waste as carbon source to prepare porous carbon with ultrahigh surface area and developing a facile protocol to synthesize supported metal nanoparticles toward an efficient formic acid (FA) decomposition are vital but remains challenging. Here, discarded ginkgo leaves were utilized as carbon source to prepare ginkgo leaf-derived porous carbon (GLPC) with an ultrahigh surface area of 3851 m²/g. Based on the as-prepared nitrogen-doped GLPC (N-GLPC) after “soft” nitriding, a facile solid-state reduction strategy with mortar-pestle grinding and without the use of any organic solvent and stabilizing ligand was developed to synthesize ultrafine and well-distributed Pd nanoparticles (NPs) with a diameter of 2.7 ± 0.7 nm. The “soft” nitriding temperature and addition of base during preparation played vital roles in the activity of the fabricated catalysts. The Pd/N-GLPC-350 exhibited the highest catalytic activity toward decomposing FA, achieving a high turnover frequency of 2952 h^?1 at 333 K. The Pd/N-GLPC-350 was quite stable and could be reused at least five times without evident activity loss. This study provides a facile solid-state reduction protocol with mortar-pestle grinding to synthesize metal NPs by using natural waste-derived porous carbon as support toward efficient FA decomposition.     

Controllable electrodeposition synthesis of Pd/TMxOy-rGO/CFP composite electrode for highly efficient methanol electro-oxidation

A novel and high-efficiency Pd/TM_xO_y-rGO/CFP (TM_xO_y = Co₃O₄, Mn₃O₄, Ni(OH)₂) electrocatalyst for directly integrated membrane electrode was synthesized by controllable cyclic voltammetry electrodeposition combined with hydrothermal process. The results showed excellent performance towards methanol oxidation reduction. The Pd/Co₃O₄-rGO/CFP as-prepared catalyst has the best electrocatalytic activity, and mass activity is 5181 mA·mg⁻¹_Pd, which is about 40 times and 4.3 times that of the commercial Pd/C and Pt/C catalyst (JM). It can be attributed that the small size of Pd nanoparticle, uniformity of distribution, and the synergistic interaction between transition metal oxide on the support surface and Pd nanoparticles. The prepared Pd/TM_xO_y-rGO/CFP composite electrode is a promising catalyst for integrated membrane electrode assembly of proton exchange membrane fuel cells in the future.