ReaxFF Molecular Dynamics Study on the Oxidative Combustion Characteristics of R1132（E）/R1234ze（E） Mixed Working Fluid

Lü Zijian; Yang Hao; Chen Yubo; Jin Tingxiang; Che Fuliang

doi:10.12465/issn.0253-4339.20260727001

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ReaxFF Molecular Dynamics Study on the Oxidative Combustion Characteristics of R1132（E）/R1234ze（E） Mixed Working Fluid

更新时间：2026-09-24

- ReaxFF Molecular Dynamics Study on the Oxidative Combustion Characteristics of R1132（E）/R1234ze（E） Mixed Working Fluid
- Journal of Refrigeration Pages: 1-13(2026)
- 作者机构：
  
  1.郑州轻工业大学能源与动力工程学院郑州 450002
  2. 河南省高效能量转化与利用国际联合实验室郑州 450002
  3. 天津商业大学农业农村部农产品低碳冷链重点实验室天津 300134
  4. 亿联鑫工程科技有限公司郑州 450000
- 作者简介：
  
  Jin Tingxiang， male， professor， Ph.D.， School of Energy and Power Engineering， Zhengzhou University of Light Industry， 86-15670626739， E-mail： txjin@126.com. Research fields： optimization of refrigeration and air-conditioning systems and application of environmentally friendly refrigerants.
- 基金信息：
- DOI：10.12465/issn.0253-4339.20260727001
  CLC： TB61⁺2;O643.2
- Received：27 July 2026，
  
  Revised：2026-08-14，
  
  Accepted：19 August 2026，
  
  Online First：24 September 2026，
- 稿件说明：
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吕子建，杨豪，陈裕博，等. R1132（E）/R1234ze（E）混合工质氧化燃烧特性的ReaxFF分子动力学研究［J］. 制冷学报，XXXX，XX（XX）：1-13.

Lü Zijian，Yang Hao，Chen Yubo，et al. ReaxFF Molecular Dynamics Study on the Oxidative Combustion Characteristics of R1132（E）/R1234ze（E） Mixed Working Fluid［J］. Journal of Refrigeration，XXXX，XX（XX）：1-13.
吕子建，杨豪，陈裕博，等. R1132（E）/R1234ze（E）混合工质氧化燃烧特性的ReaxFF分子动力学研究［J］. 制冷学报，XXXX，XX（XX）：1-13. DOI： 10.12465/issn.0253-4339.20260727001.

Lü Zijian，Yang Hao，Chen Yubo，et al. ReaxFF Molecular Dynamics Study on the Oxidative Combustion Characteristics of R1132（E）/R1234ze（E） Mixed Working Fluid［J］. Journal of Refrigeration，XXXX，XX（XX）：1-13. DOI： 10.12465/issn.0253-4339.20260727001.

摘要

为评估二元可燃工质R1132（E）/R1234ze（E）在实际应用中的安全性，采用反应分子动力学及密度泛函方法，研究温度、氧当量比、组分配比及水分子对R1132（E）/R1234ze（E）混合工质氧化燃烧行为的影响。结果表明：反应温度是控制体系反应速率的主导因素，2 000 K及以上反应物在3 000 ps内完全消耗，高温显著加速初始热解并促进后续氧化转化；氧气含量主要影响氧化深度，氧当量比由0.5增至1.5时，CO和CO

生成量显著上升，但对初始热解速率影响较小；R1132（E）/R1234ze（E）在不同组分配比中，HF的生成量基本保持恒定，约350个分子，占体系总氢含量的90%以上；较高R1234ze（E）占比会延长混合工质完全分解时间并加剧COF

生成；环境水分子通过热解提供活性自由基并捕获氟化中间体，显著促进碳完全氧化并提高HF产率。在混合体系内，R1132（E）优先通过自分解路径启动反应，而R1234ze（E）优先发生C-C键断裂生成•CF

和•C

F自由基，二者分别经COF

/COF路径和逐步C-F/C-H断裂路径最终氧化为CO

。

Abstract

Objective

R1132（E）/R1234ze（E） is a promising low-GWP binary working fluid， but both components are flammable. Leakage of the fluid during transport or operation may trigger combustion and release highly toxic fluorinated products， posing serious risks to human health and the environment. Therefore， this study aims to investigate the safety of this blended fluid in practical applications.

Methods

This study employs reactive force field （ReaxFF） molecular dynamics and density functional theory （DFT） methods to examine the effects of temperature， oxygen equiva

lence ratio， component ratio， and water molecules on the oxidative combustion behavior of the blended fluid. The DFT calculations are conducted at the M06-2X/6-311+G（d，p） level using Gaussian 16W to obtain the bond dissociation energies and bond lengths of the two fluids， and the reliability of the CHOSFClN-2014 force field is validated against the DFT results. ReaxFF simulations are performed with LAMMPS on systems containing 200 working fluid molecules together with O

， covering R1132（E）/R1234ze（E） molar ratios of 8∶2-2∶8， oxygen equivalence ratios of 0.5-1.5， and temperatures of 1 000-3 000 K； the effect of water molecules is further examined by introducing them into a specific system. The time evolution of reactants， main products， and key radicals is analyzed.

Results and Discussions

The results indicate that the oxidative combustion of R1132（E）/R1234ze（E） is initially dominated by pyrolysis， with oxygen gradually participating in the reaction at subsequent stages. Reaction temperature is the dominant factor controlling the system reaction rate： at 2 000 K and above， the reactants are completely consumed within 3 000 ps. Elevated temperatures significantly accelerate initial pyrolysis and promote subsequent oxidative conversion. Oxygen content primarily affects the oxidation depth： the yields of CO and CO

increase significantly as the oxygen equivalence ratio rises from 0.5 to 1.5， but the initial pyrolysis rate is barely affected. The component ratio regulates the reaction pathway by altering the hydrogen-to-fluorine ratio in the system； HF yield remains constant at about 350 molecules， accounting for over 90% of the total hydrogen in the system， whereas a higher proportion of R1234ze（E） prolongs the complete decomposition time of the mixed working fluid and enhances COF

formation. Environmental water molecules significantly promote complete carbon oxidation and increase HF yield by thermally dissociating to provide active radicals and captur

ing fluorinated intermediates.

Conclusions

At the molecular level， it is revealed that R1132（E） preferentially initiates reaction through a self-decomposition pathway， while R1234ze（E） preferentially undergoes C-C bond cleavage to generate ·CF

and ·C

F radicals. These intermediates are subsequently oxidized to CO

via the COF

/COF pathway and stepwise C-F/C-H dissociation pathways， respectively. This study investigates the combustion reaction mechanism of the binary flammable working fluid R1132（E）/R1234ze（E） at the microscopic scale， providing a theoretical reference for its safe application in refrigeration and air-conditioning systems.

关键词

Keywords

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