用于双功能电催化氨合成和析氧的金属-萨尔芬共价有机聚合物

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General Pub Date : 2025-05-21 DOI:10.1016/j.apcata.2025.120369

Jiani Zhao , Yuhan Xia , Wenhua Xu, You Lv, Chengbo Li, Jun Li, Ning Wang

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引用次数: 0

摘要

在此，我们报道了在M(OAc)2·nH2O （M = Co, Ni, Cu）存在下，通过希夫碱缩合1,3,5-三甲酰间苯三酚和邻苯二胺，一锅合成了金属-萨尔芬基共价有机聚合物（msalphen_cops）。FTIR光谱证实了cop通过亚胺缩合成功形成，同时揭示了一个不可逆的烯醇-酮互变异构过程，该过程推动了结构向热力学稳定框架的演变。XPS分析表明，金属离子与去质子化胺氮和羰基氧配位，不同于金属-萨尔芬配合物中传统的亚胺氮/酚氧配位。msalphen_cop对硝酸盐/亚硝酸盐还原（NOxRR）和析氧反应（OER）的电催化性能表现出强烈的金属依赖性，其中cosalphen_cop表现出优异的活性。DFT计算将钴的优势归因于它在催化循环中的最低势垒。利用其双功能，cosalphenn - cop -based NO3RR||OER系统展示了高效的NH3/O2协同生产，验证了其可持续电化学应用的潜力。这项工作为通过定制金属配体配位环境设计特定任务的cop建立了一个范例。

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Metal-Salphen covalent organic polymers for bifunctional electrocatalytic ammonia synthesis and oxygen evolution

Herein, we report a one-pot synthesis of metal-salphen-based covalent organic polymers (MSalphen-COPs) through Schiff base condensation of 1,3,5-triformylphloroglucinol and o-phenylenediamine in the presence of M(OAc)₂·nH₂O (M = Co, Ni, Cu). FTIR spectra confirm the successful formation of COPs via imine condensation while revealing an irreversible enol-keto tautomerization process that drives the structural evolution toward a thermodynamically stabilized framework. XPS analyses reveal that metal ions coordinate with deprotonated amine nitrogen and carbonyl oxygen moieties, deviating from conventional imine nitrogen/phenolate oxygen coordination in Metal-Salphen complexes. The electrocatalytic performance of MSalphen-COPs for nitrate/nitrite reduction (NO_xRR) and oxygen evolution reaction (OER) exhibits strong metal-dependent trends, with CoSalphen-COP achieving exceptional activity. DFT calculations attribute cobalt’s superiority to its lowest barriers along catalytic cycles. Leveraging its bifunctionality, a CoSalphen-COP-based NO₃RR||OER system demonstrates efficient NH₃/O₂ coproduction, validating its potential for sustainable electrochemical applications. This work establishes a paradigm for designing task-specific COPs through tailored metal-ligand coordination environments.

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来源期刊

Applied Catalysis A: General 化学-环境科学

CiteScore

9.00

自引率

5.50%

发文量

415

审稿时长

24 days

期刊介绍： Applied Catalysis A: General publishes original papers on all aspects of catalysis of basic and practical interest to chemical scientists in both industrial and academic fields, with an emphasis onnew understanding of catalysts and catalytic reactions, new catalytic materials, new techniques, and new processes, especially those that have potential practical implications. Papers that report results of a thorough study or optimization of systems or processes that are well understood, widely studied, or minor variations of known ones are discouraged. Authors should include statements in a separate section "Justification for Publication" of how the manuscript fits the scope of the journal in the cover letter to the editors. Submissions without such justification will be rejected without review.