Engineering atomic Rb-N configurations to tune radical pathways for highly selective photocatalytic H2O2 synthesis coupled with biomass valorization

IF 13.1 1区 化学 Q1 Energy
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Abstract

Photocatalytic oxygen reduction for hydrogen peroxide (H₂O₂) synthesis presents a green and cost-effective production method. However, achieving highly selective H₂O₂ synthesis remains challenging, necessitating precise control over free radical reaction pathways and minimizing undesirable oxidative by-products. Herein, we report for the visible light-driven simultaneous co-photocatalytic reduction of O2 to H2O2 and oxidation of biomass using the atomic rubidium-nitride modified carbon nitride (CNRb). The optimized CNRb catalyst demonstrates a record photoreduction rate of 8.01 mM h−1 for H2O2 generation and photooxidation rate of 3.75 mM h−1 for furfuryl alcohol to furoic acid, achieving a remarkable solar-to-chemical conversion (SCC) efficiency of up to 2.27%. Experimental characterizations and DFT calculation disclosed that the introducing atomic Rb–N configurations allows for the high-selective generation of superoxide radicals while suppressing hydroxyl free radical formation. This is because the Rb–N serves as the new alternative site to perceive a stronger connection position for O2 adsorption and reinforce the capability to extract protons, thereby triggering a high selective redox product formation. This study holds great potential in precisely regulating reactive radical processes at the atomic level, thereby paving the way for efficient synthesis of H2O2 coupled with biomass valorization.

Abstract Image

设计原子 Rb-N 构型,调整自由基途径,实现高选择性光催化 H2O2 合成及生物质增值
光催化氧还原法合成过氧化氢(H₂O₂)是一种绿色、经济的生产方法。然而,实现高选择性 H₂O₂ 合成仍然具有挑战性,需要精确控制自由基反应途径并尽量减少不良氧化副产物。在此,我们报告了利用原子铷氮化改性氮化碳(CNRb)在可见光驱动下同时共光催化将 O2 还原成 H2O2 和氧化生物质的情况。经过优化的 CNRb 催化剂在 H2O2 生成过程中的光还原速率达到创纪录的 8.01 mM h-1,在糠醇氧化成糠醛酸的过程中的光氧化速率达到 3.75 mM h-1,实现了高达 2.27% 的显著太阳能-化学转化(SCC)效率。实验表征和 DFT 计算表明,引入 Rb-N 原子构型可以高选择性地生成超氧自由基,同时抑制羟基自由基的形成。这是因为 Rb-N 可作为新的替代位点,为 O2 吸附提供更强的连接位置,并增强萃取质子的能力,从而引发高选择性氧化还原产物的形成。这项研究在原子水平上精确调节活性自由基过程方面具有巨大潜力,从而为高效合成 H2O2 以及生物质增值铺平了道路。
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来源期刊
Journal of Energy Chemistry
Journal of Energy Chemistry CHEMISTRY, APPLIED-CHEMISTRY, PHYSICAL
CiteScore
19.10
自引率
8.40%
发文量
3631
审稿时长
15 days
期刊介绍: The Journal of Energy Chemistry, the official publication of Science Press and the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, serves as a platform for reporting creative research and innovative applications in energy chemistry. It mainly reports on creative researches and innovative applications of chemical conversions of fossil energy, carbon dioxide, electrochemical energy and hydrogen energy, as well as the conversions of biomass and solar energy related with chemical issues to promote academic exchanges in the field of energy chemistry and to accelerate the exploration, research and development of energy science and technologies. This journal focuses on original research papers covering various topics within energy chemistry worldwide, including: Optimized utilization of fossil energy Hydrogen energy Conversion and storage of electrochemical energy Capture, storage, and chemical conversion of carbon dioxide Materials and nanotechnologies for energy conversion and storage Chemistry in biomass conversion Chemistry in the utilization of solar energy
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