Long Yanhui, Wang Xingzi, Zhang Hai, Wang Kaiyi, Ong Wee-Liat, Bogaerts Annemie, Li Kongzhai, Lu Chunqiang, Li Xiaodong, Yan Jianhua, Tu Xin, Zhang Hao
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China.
College of Energy Engineering, ZJU-UIUC, Zhejiang University, Hangzhou 310027, China.
JACS Au. 2024 May 8;4(7):2462-2473. doi: 10.1021/jacsau.4c00153. eCollection 2024 Jul 22.
We propose a plasma chemical looping CO splitting (PCLCS) approach that enables highly efficient CO conversion into O-free CO at mild temperatures. PCLCS achieves an impressive 84% CO conversion and a 1.3 mmol g CO yield, with no O detected. Crucially, this strategy significantly lowers the temperature required for conventional chemical looping processes from 650 to 1000 °C to only 320 °C, demonstrating a robust synergy between plasma and the CeZrO oxygen carrier (OC). Systematic experiments and density functional theory (DFT) calculations unveil the pivotal role of plasma in activating and partially decomposing CO, yielding a mixture of CO, O/O, and electronically/vibrationally excited CO*. Notably, these excited CO* species then efficiently decompose over the oxygen vacancies of the OCs, with a substantially reduced activation barrier (0.86 eV) compared to ground-state CO (1.63 eV), contributing to the synergy. This work offers a promising and energy-efficient pathway for producing O-free CO from inert CO through the tailored interplay of plasma and OCs.
我们提出了一种等离子体化学循环CO分解（PCLCS）方法，该方法能够在温和温度下将CO高效转化为无氧CO。PCLCS实现了高达84%的CO转化率和1.3 mmol g的CO产率，且未检测到氧。至关重要的是，该策略将传统化学循环过程所需的温度从650至1000°C显著降低至仅320°C，证明了等离子体与CeZrO氧载体（OC）之间强大的协同作用。系统实验和密度泛函理论（DFT）计算揭示了等离子体在激活和部分分解CO方面的关键作用，产生了CO、O/O和电子/振动激发态CO的混合物。值得注意的是，这些激发态CO物种随后在OC的氧空位上高效分解，与基态CO（1.63 eV）相比，其活化能垒大幅降低（0.86 eV），这有助于形成协同作用。这项工作通过等离子体与OC的定制相互作用，为从惰性CO中生产无氧CO提供了一条有前景且节能的途径。
