Metastable Porphyrin Assembly Engineered by Spatial Confinement for Amplified Built-In Electric Fields and High-Efficiency Photocatalytic Amino Acid Production

IF 3.4 3区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry C Pub Date : 2026-10-15 Epub Date: 2026-10-06 DOI:10.1021/acs.jpcc.6c04958

Fei Guan, Mingyang Lv, Xianggui Kong, Wenying Shi

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Abstract

Enhanced charge-separation efficiency is fundamental to advancing organic photocatalytic production of high-value amino acids from biomass feedstocks, which can be promoted by strengthening built-in electric fields (IEF). Yet, current approaches to boost IEF, relying on molecular-scale design, still cannot precisely control π-π stacking architecture, which is crucial for efficient exciton dissociation and charge-carrier extraction. Herein, the metastable Zn porphyrin living supramolecular assembly (LSA) is fabricated via layered double hydroxide. The confinement triggers highly ordered π-π stacking (spacing 3.31 Å), significantly strengthening IEF to 4.52 times that of crystalline Zn-TCPP, achieving a charge-separation efficiency of 51.7%, leading to an enzyme-free photocatalytic alanine generation rate of 103.74 μmol·g^–1·h^–1. Mechanism studies confirm photogenerated holes oxidize lactic acid to pyruvate, while exposed Zn active sites mediate electron-driven reductive amination. This confinement supramolecular strategy offers a facile route to high-performance porphyrin photocatalysts and advances sustainable sunlight-powered amino acid manufacturing.

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基于空间限制的亚稳态卟啉组装体用于放大内置电场和高效光催化氨基酸生产

提高电荷分离效率是推进生物质原料有机光催化生产高价值氨基酸的基础，而加强内置电场（IEF）可以促进这一过程。然而，目前提高IEF的方法依赖于分子尺度设计，仍然无法精确控制π-π堆叠结构，而π-π堆叠结构对于有效的激子解离和载流子提取至关重要。本文通过层状双氢氧化物制备了亚稳Zn卟啉活超分子组装体（LSA）。约束引发了高度有序的π-π层积（间距为3.31 Å），使IEF强度达到晶体Zn-TCPP的4.52倍，电荷分离效率达到51.7%，无酶光催化丙氨酸生成率达到103.74 μmol·g-1·h-1。机理研究证实，光生空穴氧化乳酸生成丙酮酸酯，而暴露的锌活性位点介导电子驱动的还原性胺化反应。这种限制超分子策略为高性能卟啉光催化剂提供了一条便捷的途径，并推进了可持续的太阳能氨基酸制造。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

The Journal of Physical Chemistry C 化学-材料科学：综合

CiteScore

6.50

自引率

8.10%

发文量

2047

审稿时长

1.8 months

期刊介绍： The Journal of Physical Chemistry A/B/C is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.