Photocatalytic Aqueous Reforming of Methyl Formate

IF 27.4 1区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Advanced Materials Pub Date : 2025-07-11 DOI:10.1002/adma.202509890

Dongxu Zuo, Suman Pradhan, Manami Banerjee, Nils Rockstroh, Stephan Bartling, Abdallah I.M. Rabee, Xinxin Tian, Alina Skorynina, Aleksander Jaworski, Laura Simonelli, Jabor Rabeah, Haijun Jiao, Matthias Beller, Shoubhik Das

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Abstract

Green hydrogen is critical to establish a sustainable energy future as it offers a clean, renewable, and a versatile alternative for decarbonizing industries, transportation, and power generation. However, the limitations of current methods significantly restrict the scope and hinder many of the envisioned applications. This study aims to report on the first example of a 3d‐metal‐based (Cu) heterogeneous photocatalytic system to produce green hydrogen via dehydrogenation of methyl formate (MF), a reaction previously known to require 4d/5d transition metals. Employing a Cu‐based atomically dispersed heterogeneous photocatalyst supported on aryl‐amino‐substituted graphitic carbon nitride (d‐gC3N4), the protocol offers numerous key advantages, including the recyclability of the photocatalyst for >10 cycles without significant activity loss, sustained hydrogen production (>15 days!) with high hydrogen yield (19.8 mmol gcat−1) and negligible CO emission, following an operationally simple, sustainable, and efficient catalytic pathway. Furthermore, the photocatalyst is characterized (using HAADF‐STEM, SS‐NMR, XAS, EPR, and XPS), all of which clearly demonstrated the presence of single atomic Cu‐site. Additionally, comprehensive mechanistic investigations together with DFT calculations allow for a thorough mechanistic rationale for this reaction. It is strongly believed that this atomically dispersed heterogeneous photocatalytic approach will open new avenues for establishing liquid organic hydrogen career (LOHC) technologies.

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光催化甲酸甲酯水溶液重整

绿色氢是建立可持续能源未来的关键，因为它为脱碳工业、运输和发电提供了清洁、可再生和多功能的替代方案。然而，当前方法的局限性极大地限制了范围并阻碍了许多设想的应用。本研究旨在报道首个基于3d金属（Cu）的非均相光催化系统通过甲酸甲酯（MF）脱氢产生绿色氢的例子，该反应以前已知需要4d/5d过渡金属。采用以芳基氨基取代石墨氮化碳（d - gC3N4）为载体的Cu基原子分散非均相光催化剂，该方案具有许多关键优势，包括光催化剂的可回收性，可循环10次而无明显活性损失，持续产氢（15天），产氢率高（19.8 mmol gcat - 1）， CO排放量可忽略不计，遵循操作简单，可持续和高效的催化途径。此外，对光催化剂进行了表征（使用HAADF - STEM， SS - NMR， XAS， EPR和XPS），所有这些都清楚地证明了单原子Cu位点的存在。此外，综合的力学研究和DFT计算允许对这种反应进行彻底的力学理论基础。相信这种原子分散非均相光催化方法将为建立液态有机氢事业（LOHC）技术开辟新的途径。

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

Advanced Materials 工程技术-材料科学：综合

CiteScore

43.00

自引率

4.10%

发文量

2182

审稿时长

2 months

期刊介绍： Advanced Materials, one of the world's most prestigious journals and the foundation of the Advanced portfolio, is the home of choice for best-in-class materials science for more than 30 years. Following this fast-growing and interdisciplinary field, we are considering and publishing the most important discoveries on any and all materials from materials scientists, chemists, physicists, engineers as well as health and life scientists and bringing you the latest results and trends in modern materials-related research every week.