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用于高电流密度下酸性析氢反应的贵金属(铂、铑、钯、铱)掺杂钌/碳纳米管超小合金

Noble Metal (Pt, Rh, Pd, Ir) Doped Ru/CNT Ultra-Small Alloy for Acidic Hydrogen Evolution at High Current Density.

作者信息

Zhang Dan, Wang Zuochao, Wu Xueke, Shi Yue, Nie Nanzhu, Zhao Huan, Miao Hongfu, Chen Xilei, Li Shaoxiang, Lai Jianping, Wang Lei

机构信息

Key Laboratory of Eco-Chemical Engineering, Key Laboratory of Optic-electric Sensing and Analytical Chemistry of Life Science, Taishan Scholar Advantage and Characteristic Discipline Team of Eco-Chemical Process and Technology, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao, 266042, P. R. China.

Shandong Engineering Research Center for Marine Environment Corrosion and Safety Protection, College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, 266042, P. R. China.

出版信息

Small. 2022 Jan;18(3):e2104559. doi: 10.1002/smll.202104559. Epub 2021 Nov 21.

Abstract

There are still great challenges to prepare high-efficiency Ru-based catalysts that are superior to Pt/C under acidic conditions, especially under high current conditions. In this work, a series of surfactant-free noble metal doped Ru/CNT (M-Ru/CNT, M = Pt, Rh, Pd, Ir, CNT stands for carbon nanotube) are prepared by microwave reduction method in 1 minute with ≈3-3.5 nm in size for the first time. In 0.5 m H SO , the overpotential of Pt-Ru/CNT (Pt: 4.94 at %) is only 12 mV. What's more, it also has much larger electrochemical surface area and intrinsic activity than Pt/C. Pt-Ru/CNT still has an ultra-small overpotential under high current density (113 mV at 500 mA cm , 155 mV at 1000 mA cm ). At the same time, it possesses excellent stability regardless of high current or low current after the durability test of 100 h. Theoretical calculation also deeply reveals that Ru is the main adsorption site of H . The comparison of the electronic structure of a series of noble metals adjusted by Ru shows that Pt has the most excellent Gibbs free energy of the adsorbed hydrogen and promotes the desorption of the product.

摘要

在酸性条件下,尤其是在高电流条件下,制备出优于Pt/C的高效钌基催化剂仍然面临巨大挑战。在本工作中,首次通过微波还原法在1分钟内制备出了一系列无表面活性剂的贵金属掺杂Ru/CNT(M-Ru/CNT,M = Pt、Rh、Pd、Ir,CNT代表碳纳米管),其尺寸约为3-3.5纳米。在0.5 M H₂SO₄中,Pt-Ru/CNT(Pt:4.94 at%)的过电位仅为12 mV。此外,它还具有比Pt/C大得多的电化学表面积和本征活性。在高电流密度下(500 mA cm⁻²时为113 mV,1000 mA cm⁻²时为155 mV),Pt-Ru/CNT仍具有超小的过电位。同时,经过100小时的耐久性测试后,无论高电流还是低电流,它都具有出色的稳定性。理论计算还深入揭示了Ru是H的主要吸附位点。一系列由Ru调节的贵金属的电子结构比较表明,Pt具有最优异的吸附氢吉布斯自由能,并促进产物的解吸。

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