质子源对双三唑吡啶铜配合物电催化析氢的影响

IF 3.3 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR
Gui-Shan Chen, Chang Liu, Xing-Jin Yang, Zhi-Hao Zhan, Tian-Shun Wang and Hua-Xin Zhang
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引用次数: 0

摘要

氢燃料的广泛利用是解决能源短缺问题的重要策略之一。因此,开发出强大的低成本高效的析氢反应催化剂是至关重要的。本文制备了一种新型二甲基吡啶-2,2 ' -(吡啶-2,6-二基双(1h -1,2,3-三唑-4,1-二基))二乙酸酯(dbes)及其铜配合物[Cu(dbes)2](ClO4)2 (Cudbes))。以乙酸(AcOH)、三氟乙酸(TFA)和对甲苯磺酸(TsOH)为质子源,研究了Cudbes在CH3CN溶液中对HER的电催化活性。AcOH、TFA和TsOH存在时,Cudbes介导的HER过电位分别为550 mV、525 mV和520 mV。法拉第效率在98%以上。AcOH组HER (kobs)的速率常数为1377 s-1,远高于TFA组(535 s-1)和TsOH组(519 s-1)。这些酸深刻地影响了Cudbes介导的HER的反应途径。AcOH介导的Cudbes催化HER遵循EECC或EEECC途径。相比之下,在TFA或TsOH存在下,催化HER遵循CEEC或CECE途径。催化反应采用质子耦合电子转移步骤和质子在dbes三唑基上的接力反应。本研究证明了双三唑吡啶是构建过渡金属配合物的良好有机支架,是很有前途的HER催化剂候选物,并为铜配合物在不同质子源下介导的HER催化提供了一些新的见解。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Effect of proton sources on the electrocatalytic hydrogen evolution reaction mediated by a copper complex of bistriazolylpyridine†

Effect of proton sources on the electrocatalytic hydrogen evolution reaction mediated by a copper complex of bistriazolylpyridine†

The widespread utilization of hydrogen fuel is one of the important strategies to fix the issues of energy shortage. It is thereby vital to develop robust, low-cost efficient catalysts for the hydrogen evolution reaction (HER). In this work, a new bistriazolylpyridine dimethyl-2,2′-(pyridine-2,6-diyl bis(1H-1,2,3-triazole-4,1-diyl))diacetate (dbes) and its copper complex [Cu(dbes)2](ClO4)2 (Cudbes) were prepared. The electrocatalytic activity of Cudbes toward the HER was studied in CH3CN solution using acetic acid (AcOH), trifluoroacetic acid (TFA), and p-toluene sulfonic acid (TsOH) as proton sources. In the presence of AcOH, TFA, and TsOH, the overpotentials for the HER mediated by Cudbes were 550 mV, 525 mV, and 520 mV, respectively. The faradaic efficiency was above 98%. The rate constant for the HER (kobs) was 1377 s−1 with AcOH, much higher than those with TFA (535 s−1) and TsOH (519 s−1). The acids profoundly affected the reaction pathways of the HER mediated by Cudbes. The catalytic HER mediated by Cudbes with AcOH followed the EECC or EEECC pathway. By contrast, in the presence of TFA or TsOH, the catalytic HER followed the CEEC or CECE pathway. The catalytic reactions invoked the proton-coupled electron transfer step and the proton relay on the triazolyl moiety of dbes. This work demonstrates that bistriazolylpyridines are good organic scaffolds to build transition metal complexes that are promising catalyst candidates for the HER and gives some new insights into the catalytic HER mediated by copper complexes using different proton sources.

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来源期刊
Dalton Transactions
Dalton Transactions 化学-无机化学与核化学
CiteScore
6.60
自引率
7.50%
发文量
1832
审稿时长
1.5 months
期刊介绍: Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.
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