Integration of multiple advantages into one catalyst: non-CO pathway of methanol oxidation electrocatalysis on surface Ir-modulated PtFeIr jagged nanowires.

Developing highly active methanol oxidation electrocatalysts with superior anti-CO poisoning capability remains a grand challenge. Herein, a simple strategy was employed to prepare distinctive PtFeIr jagged nanowires with Ir located at the shell and Pt/Fe located at the core. The Pt64Fe20Ir16 jagged nanowire possesses an optimal mass activity of 2.13 A mgPt-1 and specific activity of 4.25 mA cm-2, giving the catalyst a great edge over PtFe jagged nanowire (1.63 A mgPt-1 and 3.75 mA cm-2) and Pt/C (0.38 A mgPt-1 and 0.76 mA cm-2). The in-situ Fourier transform infrared (FTIR) spectroscopy and differential electrochemical mass spectrometry (DEMS) unravel the origin of extraordinary CO tolerance in terms of key reaction intermediates in the non-CO pathway. Density functional theory (DFT) calculations add to the body of evidence that the surface Ir incorporation transforms the selectivity from CO pathway to non-CO pathway. Meanwhile, the presence of Ir serves to optimize surface electronic structure with weakened CO binding strength. We believe this work will advance the understanding of methanol oxidation catalytic mechanism and provide some insight into structural design of efficient electrocatalysts.

Multi-sites synergistic modulation in oxygen reduction electrocatalysis.

Revealing the types of and interplays among multiple active-sites in iron-nitrogen-carbon (FeNC) materials is of great significance for developing high-performance, Fe-based non-precious metal catalysts for oxygen reduction reaction (ORR). In this paper, a single-atom FeNC catalyst is prepared through high-temperature pyrolyzing of melamine foam (MF), iron phthalocyanine (FePc), phthalocyanine (Pc), and zinc (Zn)-salts composite. The catalyst is found to contain a variety of active-sites, including carbon atom next to pyridinic-N (pyridinicNC), Fe-N4 and pore defect. It is shown that MF with high N-content is responsible for the formation of the main pyridinicNC sites and in the meantime acts as the self-sacrificed template for framework of the catalyst. The presence of Pc can facilitate the formation of the predominant Fe-N4 sites, since the interplay between Pc and FePc results in a confinement of Fe-N4. Zn-salts serve as the pore-forming additives to create sufficient pore defects which can also anchor pyridinicNC and Fe-N4 structures. The results of density functional theory (DFT) calculations suggest that the multiple active-sites function synergistically to enable high-efficiency ORR electrocatalysis. The optimal FeNC catalyst shows superior ORR activity with a half-wave potential of ∼0.88 V (vs. RHE), as well as high methanol tolerance and electrochemical stability compared to the commercial carbon-supported platinum (Pt/C) catalyst.

PtIrM (M = Ni, Co) jagged nanowires for efficient methanol oxidation electrocatalysis.

It remains a huge challenge to develop methanol oxidation electrocatalysts with remarkable catalytic activity and anti-CO poisoning capability. Herein, PtIrNi and PtIrCo jagged nanowires are successfully synthesized via a facile wet-chemical approach. Pt and Ir components are concentrated in the exterior and Ni is concentrated in the interior of PtIrNi jagged nanowires, while PtIrCo jagged nanowires feature the homogeneous distribution of constituent metals. The PtIrNi and PtIrCo jagged nanowires exhibit mass activities of 1.88 A/mgPt and 1.85 A/mgPt, respectively, 3.24 and 3.19 times higher than that of commercial Pt/C (0.58 A/mgPt). In-situ Fourier transform infrared spectroscopy indicates that CO2 was formed at a very low potential for both nanowires, in line with the high ratio of forward current density to backward current density for PtIrNi jagged nanowires (1.30) and PtIrCo jagged nanowires (1.46) relative to Pt/C (0.76). Also, the CO stripping and X-ray photoelectron spectroscopy results substantiate the remarkable CO tolerance of the jagged nanowires. Besides, the two jagged nanowires possess exceptional activities toward ethanol and ethylene glycol oxidation reactions. This work provides a novel line of thought in terms of rational design of alcohol oxidation electrocatalysts with distinctive nanostructures.

Acid-treated multi-walled carbon nanotubes as additives for negative active materials to improve high-rate-partial-state-of-charge cycle-life of lead-acid batteries.

In this work, a trace amount of acid-treated multi-walled carbon nanotubes (a-MWCNTs) is introduced into the negative active materials (NAMs) of a lead acid battery (LAB) by simply dispersing a-MWCNTs in the water, which is then added into the dry mixture of lead oxide powder, expanders and carbon black for lead paste preparation. The abundant oxygen-containing groups on the a-MWCNTs show significant influence on the chemical reactions happening during the curing process, leading to the improved properties of NAMs. Specifically, after formation, the NAMs containing 100 ppm a-MWCNTs display a spongy-like structure comprised of interconnected domino-like Pb slices, giving favorable porosity and electroactive surface area of the NAMs. Moreover, the quasi-rod structure of Pb slices provides the channels for fast electron transfer. These two features greatly accelerate the electrochemical reaction between Pb and PbSO4, and hence hinder the accumulation of PbSO4 crystals. As a result, the high-rate partial-state-of-charge (HRPSoC) cycle-life of the simulated cell constructed from the a-MWCNTs-containing negative plate achieves a HRPSoC cycle-life more than 1.5 times longer than the cell constructed when the negative plate contains only carbon black. Since our method is of great convenience and low-cost, it is expected to have a great feasibility in the LAB industry.