Unraveling ultrasonic assisted aqueous-phase one-step synthesis of porous PtPdCu nanodendrites for methanol oxidation with a CO-poisoning tolerance.

The tailored design of tri-metallic Pt-based porous nanodendrites (PNDs) is crucial for green energy production technologies, ascribed to their fancy features, great surface areas, accessible active sites, and stability against aggregation. However, their aqueous-phase one-step synthesis at room temperature remains a daunting challenge. Herein, we present a facile, green, and template-free approach for the one-step synthesis of PtPdCu PNDs by ultrasonication of an aqueous solution of metal salts and Pluronic F127 at 25 ℃, based on natural isolation among nucleation and growth step driven by the disparate reduction kinetics of the metals and acoustic cavitation mechanism of ultrasonic waves. The resultant PtPdCu PNDs formed in a spatial nanodendritic shape with a dense array of branches, open corners, interconnected pores, high surface area (46.9 m2/g), and high Cu content (21 %). The methanol oxidation reaction (MOR) mass activity of PtPdCu PNDs (3.66 mA/µgPt) is 1.45, 2.73, and 2.83 times higher than those of PtPd PNDs, PtCu PNDs, and commercial Pt/C, respectively based on equivalent Pt mass, which is superior to previous PtPdCu catalysts reported elsewhere, besides a superior durability and CO-poisoning tolerance. This study may pave the way for the controlled fabrication of ternary Pt-based PNDs for various electrocatalytic applications.

Zinc and phosphorus poisoning tolerance of Cu-SSZ-13 and Ce-Cu-SSZ-13 in the catalytic reduction of nitrogen oxides.

SSZ-13 has been commercialized as a catalyst in diesel engines for the selectivity catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3-SCR), but the catalyst is facing the problem of poisoning. Herein, two well-designed catalysts, Cu-SSZ-13 and cerium (Ce) doped Cu-SSZ-13 are synthesized, and their tolerance to zinc (Zn) and phosphorus (P) poisoning alone and together are explored in detail. The research found that Zn and P poisoning alone leads to the destruction of Cu-SSZ-13 structure, resulting in the decline of denitration (de-NOx) performance following the mechanism dominated by Eley-Rideal (E-R). Surprisingly, it is found that zinc phosphate particles are formed at inactive sites on the surface of Cu-SSZ-13 in the presence of Zn and P together, which protects the active sites, enhances the adsorption of nitric oxide. As a result, the excellent de-NOx performance of Cu-SSZ-13 is well maintained following the dual mechanism of E-R and Langmuir-Hinshelwood (L-H). In addition, the introduction of Ce stabilizes the active sites, so as to improve the de-NOx performance and the poisoning tolerance of Cu-SSZ-13. This work deeply analyzes the reasons of Zn and P poisoning and the positive effect of Ce on Cu-SSZ-13, which provides ideas for improving the poisoning tolerance of Cu-SSZ-13 and promotes the further application.

Hierarchically structured 3D carbon nanotube electrodes for electrocatalytic applications.

Hierarchically structured 3-dimensional electrodes based on branched carbon nanotubes (CNTs) are prepared on a glassy carbon (GC) substrate in a sequence of electrodeposition and chemical vapor deposition (CVD) steps as follows: Primary CNTs are grown over electrodeposited iron by CVD followed by a second Fe deposition and finally the CVD growth of secondary CNTs. The prepared 3-dimensional CNT structures (CNT/CNT/GC) exhibit enhanced double-layer capacitance and thus larger surface area compared to CNT/GC. Pt electrodeposition onto both types of electrodes yields a uniform and homogeneous Pt nanoparticle distribution. Each preparation step is followed by scanning electron microscopy, while the CNTs were additionally characterized by Raman spectroscopy. In this way it is demonstrated that by varying the parameters during the electrodeposition and CVD steps, a tuning of the structural parameters of the hierarchical electrodes is possible. The suitability of the hierarchical electrodes for electrocatalytic applications is demonstrated using the methanol electro-oxidation as a test reaction. The Pt mass specific activity towards methanol oxidation of Pt-CNT/CNT/GC is approximately 2.5 times higher than that of Pt-CNT/GC, and the hierarchical electrode exhibits a more negative onset potential. Both structures demonstrate an exceptionally high poisoning tolerance.

Ternary Pt9RhFex Nanoscale Alloys as Highly Efficient Catalysts with Enhanced Activity and Excellent CO-Poisoning Tolerance for Ethanol Oxidation.

To address the problems of high cost and poor stability of anode catalysts in direct ethanol fuel cells (DEFCs), ternary nanoparticles Pt9RhFex (x = 1, 3, 5, 7, and 9) supported on carbon powders (XC-72R) have been synthesized via a facile method involving reduction by sodium borohydride followed by thermal annealing in N2 at ambient pressure. The catalysts are physically characterized by X-ray diffraction, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy, and their catalytic performance for the ethanol oxidation reaction (EOR) is evaluated by cyclic and linear scan voltammetry, CO-stripping voltammograms, and chronopotentiometry. All the Pt9RhFex/C catalysts of different atomic ratios produce high EOR catalytic activity. The catalyst of atomic ratio composition 9:1:3 (Pt/Rh/Fe) has the highest activity and excellent CO-poisoning tolerance. Moreover, the enhanced EOR catalytic activity on Pt9RhFe3/C when compared to Pt9Rh/C, Pt3Fe/C, and Pt/C clearly demonstrates the presence of Fe improves catalytic performance. Notably, the onset potential for CO oxidation on Pt9RhFe3/C (0.271 V) is ∼55, 75, and 191 mV more negative than on Pt9Rh/C (0.326 V), Pt3Fe/C (0.346 V), and Pt/C (0.462 V), respectively, which implies the presence of Fe atoms dramatically improves CO-poisoning tolerance. Meanwhile, compared to the commercial PtRu/C catalyst, the peak potential on Pt9RhFe3/C for CO oxidation was just slightly changed after several thousand cycles, which shows high stability against the potential cycling. The possible mechanism by which Fe and Rh atoms facilitate the observed enhanced performance is also considered herein, and we conclude Pt9RhFe3/C offers a promising anode catalyst for direct ethanol fuel cells.