Metal-Free Electrocatalytic Alkaline Water Splitting by Porous Macrocyclic Proton Sponges

IF 16.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Ananda Basak, Arun Karmakar, Sayantani Dutta, Diptendu Roy, Satyadip Paul, Yusuke Nishiyama, Biswarup Pathak, Subrata Kundu, Rahul Banerjee
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引用次数: 0

Abstract

Macrocycles are unique as they encapsulate and transfer guest molecules or ions and facilitate catalytic processes. Although metalated macrocycles are pivotal in electrocatalytic processes, using metal-free analogs has been rare. Following the strategy of Kanbara et al., we synthesized an azacalixarene macrocycle— N, N’, N’’-tris(p-aminophenyl)azacalix[3](2,6)pyridine (CalixNH2). The macrocycle encapsulates a proton in its cavity, maintaining the protonation even in highly alkaline media. Notably, it retains almost 50% protonated form in 1 M KOH (~pH 14)—acting as a proton sponge. As hydrogen evolution is complex in alkaline media owing to sluggish water dissociation, we implemented the proton sponge (CalixNH2) in an alkaline hydrogen evolution reaction. Conjugated Porous polymers, TpCalix and DhaCalix, have been synthesized from the triamine—CalixNH2. The most efficient catalyst, TpCalix, has shown excellent performance in alkaline HER and OER in 1 M KOH (~pH 14), with low overpotentials of only 112(±2) and 290(±2) mV at 10 mA cm-2, respectively, and durable up to 24 hours. A full-cell reaction using TpCalix in both the cathode and anode exhibited a low full-cell voltage of 1.73 V and was stable for 12 hours. DFT calculations verified the tripyridinic core, which acts as the principal site for proton abstraction and binding.
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来源期刊
CiteScore
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
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