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Moskyon木蟲 (初入文壇)
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[求助]
關(guān)于HER的tafel測量問題 已有1人參與
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本人電化學(xué)小白，最近在析氫測試，對于tafel斜率會進(jìn)行擬合，但是對lsv的正負(fù)掃向問題很疑惑。 我知道析氫測試的lsv極化曲線是進(jìn)行負(fù)掃，但看到有說tafel的擬合需要通過lsv正掃計(jì)算，通過測試這兩者的擬合結(jié)果存在出入 負(fù)掃的tafel會更小一些。 那究竟正掃負(fù)掃哪個是正確的，為什么會存在出入呢，如果可以請幫我找到參考文獻(xiàn)，謝謝大家了！ @Gamry-電化學(xué) @langzhizhou @louderbe 發(fā)自小木蟲Android客戶端 |
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Moskyon
木蟲 (初入文壇)
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2樓2018-03-21 15:24:50
3樓2018-03-27 01:14:08
Gamry-電化學(xué) 
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【答案】應(yīng)助回帖
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首先， 對電位的正負(fù)規(guī)定，歐洲和美國的科學(xué)家，尤其在電催化領(lǐng)域，有些不同，看下面的介紹： https://en.wikipedia.org/wiki/El ... al#Sign_conventions Sign conventions Historically, two conventions for sign for the electrode potential have formed:[2] convention "Nernst–Lewis–Latimer" (sometimes referred to as "American"  ,convention "Gibbs–Ostwald–Stockholm" (sometimes referred to as "European" .In 1953 in Stockholm[3] IUPAC recognized that either of the conventions is permissible; however, it unanimously recommended that only the magnitude expressed according to the convention (2) be called "the electrode potential". To avoid possible ambiguities, the electrode potential thus defined can also be referred to as Gibbs–Stockholm electrode potential. In both conventions, the standard hydrogen electrode is defined to have a potential of 0 V. Both conventions also agree on the sign of E for a half-cell reaction when it is written as a reduction. The main difference between the two conventions[4] is that upon reversing the direction of a half-cell reaction as written, according to convention (1) the sign of E also switches, whereas in convention (2) it does not. The logic behind switching the sign of E is to maintain the correct sign relationship with the Gibbs free energy change, given by ΔG = -nFE where n is the number of electrons involved and F is the Faraday constant. It is assumed that the half-reaction is balanced by the appropriate SHE half-reaction. Since ΔG switches sign when a reaction is written in reverse, so to, proponents of convention (1) argue, should the sign of E. Proponents of convention (2) argue that it is more convenient to consider oxidants and reductants on the same scale. （2） 把BARD的JACS一篇文章， 放上，看其中的一種說法：析氫測試的lsv極化曲線是進(jìn)行負(fù)掃: First, the MoS2 substrate potential was swept from 0 V to − 0.7 V at a scan rate of 5 mV/s to generate hydrogen continuously, and the hydrogen was then collected at the Pt UME tip. https://pdfs.semanticscholar.org ... 7029b2749dc3581.pdf 歡迎其他專家給出見解。 |
4樓2018-03-27 03:21:11
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