Nitrogen-doped carbon black supported synergistic palladium single atoms and nanoparticles for electrocatalytic oxidation of methanol

Interface engineering of Ni/NiO heterostructures with abundant catalytic active sites for enhanced methanol oxidation electrocatalysis.

Introducing oxophilic metals into Pt‐based alloy catalysts can effectively alleviate the poisoning by CO intermediates (CO*) during methanol oxidation reactions (MOR). However, excessive oxophilic metals on the surface of catalysts tend to form thermodynamically stable carbonyl compound‐like structures, occupying electrocatalytically active sites, which is not conducive to the enhancement of catalytic activity. Herein, a kind of surface segregated FePtRh nanoflowers for effectively eliminating the CO* poisoning during MOR electrocatalysis is presented. The FePtRh nanoflowers are constituted by the Rh‐rich core and Fe‐rich shell. The optimized Fe21Pt66Rh13/C shows a high mass activity of 3.90 A mgPt−1 and a specific activity of 4.85 mA cm−2. It is confirmed that the electron transfer from Pt to Rh or Fe atoms is beneficial for the higher anti‐CO poisoning ability, which mainly originate from the alloying of Rh atoms and surface‐segregated structures. Density functional theory calculations reveal the decreased electrons adsorbed by CO* on both Pt–Pt bridge sites and top sites weakens the strong adsorption energy between Pt atoms and CO* intermediates. The optimal nanoflowers also show excellent performance toward ethanol oxidation reaction (EOR) with a high mass activity of 2.76 A mgPt−1 and the enhanced anti‐CO poisoning ability, as well as the improved stability.

Anti‐CO Poisoning FePtRh Nanoflowers with Rh‐Rich Core and Fe‐Rich Shell Boost Methanol Oxidation Electrocatalysis

PdMoSb trimetallene as high-performance alcohol oxidation electrocatalyst

Innovative and facile methods for the preparation of metal nanoparticles (MNPs) with A highly uniform distribution and anchored on a unique substrate are receiving increasing interest for the development of efficient and low-cost catalysts in the field of alternative and sustainable energy technologies. In this study, we report a novel and facile metal-ions adsorption-pyrolysis method based on a hydrogel nanocomposite for the preparation of well-distributed nickel nanoparticles on 3D porous carbon frameworks (Ni@PCFs). The pyrolysis temperature effect on electrocatalytic activity toward methanol oxidation and catalyst stability was investigated. Physicochemical characterizations (SEM, TEM, and XRD) were used to determine the morphology and composition of the prepared electrocatalyst, which were then linked to their electrocatalytic activity. The experimental results indicate that the catalyst synthesized by pyrolysis at 800 °C (Ni@PCFs-8) exhibits the highest electrocatalytic activity for oxidation of methanol in alkaline media. Additionally, prepared Ni@PCFs-8 displays a remarkable increase in electrocatalytic activity after activation in 1 M KOH and excellent stability. The adsorption-pyrolysis pathway ensures that the Ni NPs are trapped in the PCFs, which can provide highly reactive surface sites. This work may provide a facile and effective strategy for preparing uniformly distributed metallic NPs on a 3D PCF substrate with high catalytic activity for energy applications.

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Hydrogel Nanocomposite-Derived Nickel Nanoparticles/Porous Carbon Frameworks as Non-Precious and Effective Electrocatalysts for Methanol Oxidation

Alkaline direct alcohol fuel cells (ADAFCs) represent an attractive alternative to hydrogen fuel cells for the more convenient storage, transportation, and lower cost of alcohols (e.g., methanol and ethanol) when compared with compressed hydrogen. However, the anode alcohol oxidation reaction (AOR) is generally plagued with high overpotential and sluggish kinetics, and often requires noble metal‐based electrocatalysts to accelerate the reaction kinetics. To this end, the development of efficient AOR electrocatalysts with high mass activity (MA), high durability, high Faradaic efficiency (FE), and low overpotential is central for realizing practical ADAFCs. Here, in this minireview, a brief introduction of the fundamental challenges associated with AOR in alkaline electrolyte, the key performance metrics, and the evaluation protocols for benchmarking AOR electrocatalysts are presented, followed by a summary of the recent advances in the noble‐metal based AOR electrocatalysts (e.g., Pt, Pd, and Rh) with an emphasis on the design criteria for improving the specific activity and electrochemical surface area to ultimately deliver high MA while at the same time ensuring long term durability. The strategies to enhance FE and lower overpotential will also be discussed. Last, it is concluded with a brief perspective on the key challenges and future opportunities.

Noble Metal Based Electrocatalysts for Alcohol Oxidation Reactions in Alkaline Media

Hydrazine‐assisted water electrolysis offers a feasible path for low‐voltage green hydrogen production. Herein, the design and synthesis of ultrathin RhRu0.5‐alloy wavy nanowires as bifunctional electrocatalysts for both the anodic hydrazine oxidation reaction (HzOR) and the cathodic hydrogen evolution reaction (HER) is reported. It is shown that the RhRu0.5‐alloy wavy nanowires can achieve complete electrooxidation of hydrazine with a low overpotential and high mass activity, as well as improved performance for the HER. The resulting RhRu0.5 bifunctional electrocatalysts enable, high performance hydrazine‐assisted water electrolysis delivering a current density of 100 mA cm−2 at an ultralow cell voltage of 54 mV and a high current density of 853 mA cm−2 at a cell voltage of 0.6 V. The RhRu0.5 electrocatalysts further demonstrate a stable operation at a high current density of 100 mA cm−2 for 80 hours of testing period with little irreversible degradation. The overall performance greatly exceeds that of the previously reported hydrazine‐assisted water electrolyzers, offering a pathway for efficiently converting hazardous hydrazine into molecular hydrogen.

Xiaoyang Fu

Papers

Noble Metal Based Electrocatalysts for Alcohol Oxidation Reactions in Alkaline Media

Bifunctional Ultrathin RhRu0.5‐Alloy Nanowire Electrocatalysts for Hydrazine‐Assisted Water Splitting