Reaction Mechanism and Hydrogen Production Efficiency of the Aluminum-Water Reaction in Sub/Supercritical Water

XU Yuhao; WU Zongjian; YUAN Ming; SUN Wuchuan; HUANG Zuohua; CHEN Di; SHE Yong; ZHANG Yingjia

doi:10.7652/xjtuxb202608009

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Reaction Mechanism and Hydrogen Production Efficiency of the Aluminum-Water Reaction in Sub/Supercritical Water

更新时间：2026-07-28

- Reaction Mechanism and Hydrogen Production Efficiency of the Aluminum-Water Reaction in Sub/Supercritical Water
- Journal of Xi'an Jiaotong University Vol. 60, Issue 8, Pages: 102-111(2026)
- 作者机构：
  
  西安交通大学绿色氢电全国重点实验室，710049，西安
  内蒙机械动力研究所，010010，呼和浩特
- 作者简介：
- 基金信息：
- DOI：10.7652/xjtuxb202608009
  CLC： TK91
- Received：13 January 2025，
  
  Online First：02 April 2026，
  
  Published：10 August 2026
- 稿件说明：
移动端阅览
XU Yuhao, WU Zongjian, YUAN Ming, et al. Reaction Mechanism and Hydrogen Production Efficiency of the Aluminum-Water Reaction in Sub/Supercritical Water[J]. Journal of Xi'an Jiaotong University, 2026, 60(8): 102-111.
DOI：

XU Yuhao, WU Zongjian, YUAN Ming, et al. Reaction Mechanism and Hydrogen Production Efficiency of the Aluminum-Water Reaction in Sub/Supercritical Water[J]. Journal of Xi'an Jiaotong University, 2026, 60(8): 102-111. DOI： 10.7652/xjtuxb202608009.

摘要

为揭示亚/超临界水对铝水反应制氢效率的影响规律及其作用机制，针对多物理场耦合作用下反应机制尚不明确的问题，搭建了高温高压反应釜实验平台，采用电子扫描电镜（SEM）和X射线衍射（XRD）等手段，系统分析了固相产物的物相组成与微观形貌，探究了铝颗粒表面钝化层破裂机制，阐明了铝颗粒粒径、反应温度、介质密度及超临界水环境对产氢能力的影响规律。结果表明：铝水反应产物具有显著的温度与密度依赖性，在400～600 K液态水中主要生成AlOOH，仅在低温下（400 K）存在少量Al（OH）

与未反应铝，而在773 K超临界水中完全转化为Al

；铝粉粒径对铝水反应制氢过程具有显著影响，随粒径由154μm降低至12μm，反应起始温度和完全反应温度均明显降低。完全反应温度由600 K降低至380 K；在600 K条件下，52 μm与154 μm铝粉在液态水中的制氢效率分别为95.1%和92.5%，显著高于水蒸气环境下的78.9%和49.2%；正庚烷包覆铝粉在亚临界水中基本不反应，而在超临界水中690 K时制氢效率达到70.3%。研究结果表明，细化颗粒可显著降低反应温度，液态水、超临界水环境能有效提升铝粉反应活性。该研究揭示了不同环境下铝水反应路径及产物演化差异，可为铝基材料制氢反应过程优化、反应器设计及机理模型构建提供理论依据，为铝基材料低温高效制氢的发展提供研究思路。

Abstract

To elucidate the influence of subcritical and supercritical water on the hydrogen production efficiency of the aluminum-water reaction and its underlying mechanism

and to address the currently unclear reaction mechanism under coupled multi-physics fields

a high-temperature and high-pressure sealed batch reactor system was established

and scanning electron microscopy (SEM) and X-ray diffraction (XRD) were employed to systematically characterize the phase composition and microstructure of the solid products. The rupture mechanism of the passivation layer on aluminum particles was investigated

and the effects of particle size

reaction temperature

medium density

and supercritical water environment on hydrogen production performance were clarified. The results show that the reaction products exhibit strong temperature and density dependence. In liquid water at 400—600 K

AlOOH is the dominant product

with minor amounts of Al (OH)

and unreacted aluminum observed only at 400 K.In contrast

the product transforms completely into Al

in supercritical water at 773 K.Aluminum particle size significantly influences the hydrogen production performance of the Al-water reaction. Reducing the particle size from 154μm to 12μm significantly decreases both the onset reaction temperature and complete reaction temperature

with the latter decreasing from 600 K to 380 K.At 600 K

the hydrogen production efficiencies of 52 μm and 154μm aluminum powders in liquid water are 95.1% and 92.5%

respectively

which are significantly higher than those in water vapor (78.9% and 49.2%) .Heptane-coated aluminum particles exhibit negligible reactivity in subcritical water

whereas a high hydrogen production efficiency of 70.3% is achieved at 690 K in supercritical water. These findings indicate that particle refinement significantly reduces the reaction temperature

while liquid water and supercritical water environments effectively enha

nce the reactivity of the aluminum powder. Moreover

the reaction pathways and product evolution of the aluminum-water system differ under various environments

providing a theoretical basis for optimizing hydrogen production processes based on aluminum materials

for reactor design

and for mechanistic model development

and offering new insights for achieving low-temperature

high-efficiency hydrogen production from aluminum-based materials.

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references

刘光明，解东来.铝水反应制氢技术研发进展[J].电源技术，2011，35（1）：109-112.

Liu Guangming, Xie Donglai. Advance of hydrogen production from aluminum water reaction[J]. Chinese Journal of Power Sources, 2011, 35 (1): 109-112.

Bergthorson J M.Recyclable metal fuels for clean and compact zero-carbon power [J].Progress in Energy and Combustion Science,2018,68:169-196.

周勇，姬雄帅，李航，等.铝基材料水解制氢技术研究进展[J].中国材料进展，2024，43（5）：429-439.

Zhou Yong, Ji Xiongshuai, Li Hang, et al. Research progress on hydrogen production technology for aluminum-based materials[J]. Materials China, 2024, 43 (5)：429-439.

Saceleanu F, Vuong T V, Master E R, et al. Tunable kinetics of nanoaluminum and microaluminum powders reacting with water to produce hydrogen [J].International Journal of Energy Research,2019,43:7384-7396.

杨阳，邓振炎，郭晓晗，等.改性铝在制氢及去除水中污染物中的应用[J].华东师范大学学报（自然科学版），2023（2）：168-182.

Yang Yang, Deng Zhenyan, Guo Xiaohan, et al. Surface-modified aluminum used for hydrogen generation and aqueous contaminant removal[J]. Journal of East China Normal University (Natural Sciences), 2023 (2)：168-182.

刘昊，孙立贤，徐芬，等.高活性A-l LiBH4-Bi铝基复合制氢材料[J].电源技术，2015，39（11）：2409-2411.

Liu Hao, Sun Lixian, Xu Fen, et al. High active A1-LiBH4-Bi composite for hydrogen generation[J]. Chinese Journal of Power Sources, 2015, 39 (11)：2409-2411.

Zhang Xiaoliang, Fang Jiawei, Feng Yao, et al. The mechanism of water decomposition on surface of alumi num and gallium alloy during the hydrogen production process:a DFT study [J].International Journal of Hydrogen Energy,2024,66:354-361.

Wang Hongchao, Ma Huanhuan, Jin Zhijiang, et al. Sn-free Al-based on-demand hydrogen production materials for easy recycling [J].International Journal of Hydrogen Energy,2024,49（Part A）:1332-1343.

Chen Yiting, Huang Liangying, Wang Hongwen. Optimization of aluminum hydroxide catalyst for efficient hydrogen generation from aluminum-water reaction [J]. International Journal of Hydrogen Energy,2024,91：303-309.

Ambaryan G N, Vlaskin M S, Dudoladov A O, et al. Hydrogen generation by oxidation of coarse aluminum in low content alkali aqueous solution under intensive mixing [J].International Journal of Hydrogen Energy,2016,41（39）:17216-17224.

Yavor Y, Goroshin S, Bergthorson J M, et al. Enhanced hydrogen generation from aluminum-water reactions [J].International Journal of Hydrogen Energy,2013,38（35）:14992-15002.

Vlaskin M S, Shkolnikov E I, Bersh A V.Oxidation kinetics of micron-sized aluminum powder in high-temperature boiling water [J].International Journal of Hydrogen Energy,2011,36（11）:6484-6495.

Trowell K A, Goroshin S, Frost D L, et al. The use of supercritical water for the catalyst-free oxidation of coarse aluminum for hydrogen production [J].Sustainable Energy & Fuels,2020,4（11）:5628-5635.

Trowell K A, Goroshin S, Frost D L, et al. Hydrogen production rates of aluminum reacting with varying densities of supercritical water [J].RSC Advances, 2022,12（20）:12335-12343.

欧国标，任一飞，金辉，等.典型煤种超临界水气化动力学模型[J].工程热物理学报，2022，43（8）：2009-2018.

Ou Guobiao, Ren Yifei, Jin Hui, et al. Kinetic model for supercritical water gasification of typical coals[J]. Journal of Engineering Thermophysics, 2022, 43 (8)：2009-2018.

Deng Zhenyan, Ferreira J, Tanaka Y, et al. Physicochemical mechanism for the continuous reaction of g-Al 2 O 3 modified Al powder with water [J ] .Journal of the American Ceramic Society, 2007, 90（5）：1521-1526.

Deng Zhenyan, Liu Yufu, Tanaka Y, et al. Modification of Al particle surfaces by g-Al 2 O 3 and its effect on the corrosion behavior of Al [J ] .Journal of the Ameri can Ceramic Society,2005,88（4）:977-979.

Gao Xinyue, Wang Chang'an, Hou Yujie, et al. Experimental study on characteristics and mechanism of hydrogen production from aluminium-water reaction for carbon-free power generation [J].Fuel,2025, 380:133206.

Bunker B C, Nelson G C, Zavadil K, et al. Hydration of passive oxide films on aluminum [J].Journal of Physical Chemistry: B,2002,106（18）:4705-4713.

Mezulis A, Richter C, Lesnicenoks P, et al. Studies on water-aluminum scrap reaction kinetics in two steps and the efficiency of green hydrogen production [J]. Energies,2023,16（14）:5554.

Gai Weizhuo, Liu Wenhui, Deng Zhenyan, et al. Reaction of Al powder with water for hydrogen generation under ambient condition [J].International Journal of Hydrogen Energy,2012,37（17）:13132-13140.

Galkin A A, Lunin V V.Subcritical and supercritical water:a universal medium for chemical reactions [J]. Russian Chemical Reviews,2005,74（1）:21-35.

Vedder W, Vermilyea D A.Aluminum + water reaction [J].Transactions of the Faraday Society,1969, 65:561-584.

Mizan T I, Savage P E, Ziff R M.Temperature dependence of hydrogen bonding in supercritical water [J].The Journal of Physical Chemistry, 1996, 100（1）:403-408.

郑豪，鱼涛，屈撑囤，等.超临界水的基本特性及应用进展[J].化工技术与开发，2020，49（2/3）：62-66.

Zheng Hao, Yu Tao, Qu Chengtun, et al. Basic Characteristics and Application Advances of Supercritical Water[J]. Technology and Development of Chemical Industry, 2020, 49 (2/3): 62-66.

郝小红，郭烈锦，吕友军，张西民.生物质超临界水气化制氢反应动力学分析[J].西安交通大学学报，2005, 39（7）:681-684 Hao Xiaohong, Guo Liejin, Lu Youjun, et al. Reaction kinetics analysis of hydrogen production by biomass gasification in supercritical water[J].Journal of Xi'an Jiaotong University，

续京.超临界水与环境保护[J].化工装备技术，2006，27（4）：63-66.

Xu Jing. Supercritical water and environmental protection[J]. Chemical Equipment Technology, 2006, 27 (4): 63-66.

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