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通过钴调制抑制用于高耐一氧化碳燃料电池阳极催化剂的电子回授

Suppressing Electron Back-Donation for a Highly CO-tolerant Fuel Cell Anode Catalyst via Cobalt Modulation.

作者信息

Yang Yu, Gao Fei-Yue, Zhang Xiao-Long, Qin Shuai, Zheng Li-Rong, Wang Ye-Hua, Liao Jie, Yang Qing, Gao Min-Rui

机构信息

Division of Nanomaterials & Chemistry, Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, 230026, Hefei, China.

Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, 100049, Beijing, China.

出版信息

Angew Chem Int Ed Engl. 2022 Oct 17;61(42):e202208040. doi: 10.1002/anie.202208040. Epub 2022 Jul 28.

Abstract

Platinum on carbon (Pt/C) catalyst is commercially adopted in fuel cells but it undergoes formidable active-site poisoning by carbon monoxide (CO). In particular, given the sluggish kinetics of hydrogen oxidation reaction (HOR) in anion-exchange membrane fuel cell (AEMFC), the issues of Pt poisoning and slow rate would combine mutually, notably worsening the device performances. Here we overcome these challenges through incorporating cobalt (Co) into molybdenum-nickel alloy (MoNi ), termed Co-MoNi , which not only shows superior HOR activity over the Pt/C catalyst in alkali, but more intriguingly exhibits excellent CO tolerance with only small activity decay after 10 000 cycles in the presence of 500 parts per million (ppm) CO. When feeding with CO (250 ppm)/H , the AEMFC assembled by this catalyst yields a peak power density of 394 mW cm , far exceeding the Pt/C catalyst. Experimental and computational studies reveal that weakened CO chemisorption originates from the electron-deficient Ni sites after Co incorporation that suppresses d→CO 2π* back-donation.

摘要

铂碳(Pt/C)催化剂在燃料电池中已被商业应用,但它会遭受一氧化碳(CO)导致的严重活性位点中毒。特别是,鉴于阴离子交换膜燃料电池(AEMFC)中氢氧化反应(HOR)的动力学缓慢,Pt中毒和反应速率缓慢的问题会相互叠加,显著恶化器件性能。在此,我们通过将钴(Co)掺入钼镍合金(MoNi)中,即Co-MoNi,克服了这些挑战,它不仅在碱性条件下比Pt/C催化剂表现出更优异的HOR活性,更有趣的是,在存在百万分之500(ppm)CO的情况下,经过10000次循环后,其活性仅略有下降,展现出优异的CO耐受性。当通入CO(250 ppm)/H₂时,由这种催化剂组装的AEMFC产生的峰值功率密度为394 mW cm⁻²,远远超过Pt/C催化剂。实验和计算研究表明,CO化学吸附减弱源于掺入Co后电子缺乏的Ni位点,从而抑制了d→CO 2π*反馈π键。

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