Wang Jing, Hong Yingshan, Li Tong, Zhang Zhijun, Xie Yuanhua, Han Jin, Jiang Xi Zhuo
School of Mechanical Engineering and Automation, Northeastern University, Shenyang 110819, China.
ACS Omega. 2025 Jul 25;10(30):33921-33931. doi: 10.1021/acsomega.5c04941. eCollection 2025 Aug 5.
Ammonia (NH) is increasingly recognized as an important sustainable energy carrier, and methane (CH) is typically added to combustion systems to enhance their combustion performance. Reaction pathways of NH/CH combustion require further clarification. In the present study, the key reactions of NH oxidation and NO formation in NH/CH combustion were revealed at the subatomic level. The CCSD-(T)/cc-pvqz//B3LYP/6-311 + G-(d,p) and CBS-QB3 methods were used to calculate the molecular structures, transition states, and energy barriers of all reactions. The rate constants were calculated by the transition state theory with the Wigner tunneling correction, and the results in the present study agree well with previous experimental data and theoretical calculation. Moreover, rate constants were fitted to the Arrhenius equation over the temperature range of 300-2500 K to obtain activation energies. Notably, rate constants and activation energies were determined for the reactions (NH + CH → NH + CH and HNO + HO → NO + HO) that were revealed by the present study. This study will contribute to the understandings of fuel performance in the new era for sustainable energy.
氨（NH₃）日益被视为一种重要的可持续能源载体，而甲烷（CH₄）通常被添加到燃烧系统中以提高其燃烧性能。NH₃/CH₄燃烧的反应途径需要进一步阐明。在本研究中，在亚原子水平揭示了NH₃/CH₄燃烧中NH₃氧化和NO形成的关键反应。采用CCSD-(T)/cc-pvqz//B3LYP/6-311+G-(d,p)和CBS-QB3方法计算了所有反应的分子结构、过渡态和能垒。通过带有维格纳隧穿校正的过渡态理论计算速率常数，本研究结果与先前的实验数据和理论计算结果吻合良好。此外，在300 - 2500 K的温度范围内将速率常数拟合到阿伦尼乌斯方程以获得活化能。值得注意的是，本研究揭示的反应（NH₂ + CH₄ → NH₃ + CH₃和HNO + H₂O → NO + H₂O）的速率常数和活化能也已确定。本研究将有助于理解可持续能源新时代的燃料性能。
