DRIFTS-SSITKA-MS investigations on the mechanism of plasmon preferentially enhanced CO2 hydrogenation over Au/?-Al2O3
DRIFTS-SSITKA-MS investigations on the mechanism of plasmon preferentially enhanced CO2 hydrogenation over Au/?-Al2O3
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DRIFTS-SSITKA-MS 研究等离激元优先增强 CO2 氢化的机制
DOI：
10.1016/j.apcatb.2023.122531
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Wang K
中科院分区：
文献类型：
--
作者：
Wang K
局域等离子体共振（LSPR）被认为是一种有效的方式来转换入射光的能量和显着提高催化反应。然而，对等离子体激元-热耦合机制的全面理解仍然缺乏。为了解决这一知识空白，我们研究了Au/γ-Al 2 O3上光热耦合催化逆水煤气变换反应的反应途径和等离子体增强机理.结果表明，甲酸和羧基途径有助于整个反应。在低反应温度下，小Au NPs的间甲酸途径被建议为主要的反应机理。光谱动力学和理论计算分析表明，等离子体激元能量优先转移到HCOO* 通过热电子和共振能量转移机制的组合。等离子体激元能量促进HCOO* 脱水为CO，这是整个RWGS反应的速率决定步骤（RDS）。
The localized plasmon resonance (LSPR) is recognized as an effective way to convert incident light energy and significantly boost the catalytic reaction. However, a comprehensive understanding of the plasmon-thermo coupling mechanism is still lacking. To address this knowledge gap, we investigate reaction pathway and plasmonic enhancement mechanism of the photo-thermo coupled catalytic reverse water gas shift (RWGS) reactions over Au/γ-Al2O3. The results indicate that both formate and carboxyl pathways contribute to the overall reaction. The m-formate pathway is suggested as the main reaction mechanism at low reaction temperature over small Au NPs. Spectro-kinetics and theoretical calculation analyses indicate that the plasmonic energy preferentially transfers to HCOO* via a combination of hot electron and resonance energy transfer mechanisms. The plasmonic energy facilitates the dehydration of HCOO* to CO, which is the rate-determining step (RDS) of the overall RWGS reaction.