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揭示Cu/γ-AlO催化剂上等离子体催化低温水煤气变换反应的机理

Unveiling the Mechanism of Plasma-Catalytic Low-Temperature Water-Gas Shift Reaction over Cu/γ-AlO Catalysts.

作者信息

Shen Xiaoqiang, Craven Michael, Xu Jiacheng, Wang Yaolin, Li Zhi, Wang Weitao, Yao Shuiliang, Wu Zuliang, Jiang Nan, Zhou Xuanbo, Sun Kuan, Du Xuesen, Tu Xin

机构信息

Key Laboratory of Low-Grade Energy Utilization Technologies and Systems, Ministry of Education, Chongqing University, Chongqing 400044, China.

School of Energy and Power Engineering, Chongqing University, Chongqing 400044, China.

出版信息

JACS Au. 2024 Aug 13;4(8):3228-3237. doi: 10.1021/jacsau.4c00518. eCollection 2024 Aug 26.

Abstract

The water-gas shift (WGS) reaction is a crucial process for hydrogen production. Unfortunately, achieving high reaction rates and yields for the WGS reaction at low temperatures remains a challenge due to kinetic limitations. Here, nonthermal plasma coupled to Cu/γ-AlO catalysts was employed to enable the WGS reaction at considerably lower temperatures (up to 140 °C). For comparison, thermal-catalytic WGS reactions using the same catalysts were conducted at 140-300 °C. The best performance (72.1% CO conversion and 67.4% H yield) was achieved using an 8 wt % Cu/γ-AlO catalyst in plasma catalysis at ∼140 °C, with 8.74 MJ mol energy consumption and 8.5% H fuel production efficiency. Notably, conventional thermal catalysis proved to be ineffective at such low temperatures. Density functional theory calculations, coupled with diffuse reflectance infrared Fourier transform spectroscopy, revealed that the plasma-generated OH radicals significantly enhanced the WGS reaction by influencing both the redox and carboxyl reaction pathways.

摘要

水煤气变换(WGS)反应是制氢的关键过程。不幸的是,由于动力学限制,在低温下实现WGS反应的高反应速率和产率仍然是一个挑战。在此,采用非热等离子体与Cu/γ -Al₂O₃催化剂耦合,以使WGS反应能在相当低的温度(高达140°C)下进行。为作比较,使用相同催化剂的热催化WGS反应在140 - 300°C下进行。在等离子体催化中,使用8 wt%的Cu/γ -Al₂O₃催化剂在约140°C下实现了最佳性能(CO转化率72.1%,H₂产率67.4%),能耗为8.74 MJ/mol,H₂燃料生产效率为8.5%。值得注意的是,传统热催化在如此低的温度下被证明是无效的。密度泛函理论计算与漫反射红外傅里叶变换光谱相结合表明,等离子体产生的OH自由基通过影响氧化还原和羧基反应途径显著增强了WGS反应。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f38a/11350726/087e4b91a956/au4c00518_0001.jpg

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