SHUI Jianglan， GAO Sai， LIU Ruonan， et al. MXene hydrogen storage： theoretical and experimental research results and future outlook［J］. China Powder Science and Technology，2025，31（5）：1−11.

DOI：10.13732/j.issn.1008-5548.2025.05.001

收稿日期： 2024-12-30，修回日期： 2025-03-10，上线日期： 2025-04-03。

基金项目： 国家重点发计划项目，编号 ：2021YFB4000601；国家自然科学基金项目，编号：U21A20328，2225903。

第一作者简介： 水江澜（1977—），男，教授，博士，博士生导师，国家杰出青年基金获得者，研究方向为质子膜燃料电池电催化剂与膜电极、储氢材料、能源化学电催化剂。E-mail：shuijianglan@buaa.edu.cn。

摘要： 【目的】 梳理二维材料MXene在储氢中的理论和实验研究结果，为氢能源的高效应用和存储安全提供参考。【研究现状】 综述MXene结构和储氢应用、理论研究结果、实验研究结果，MXene具有表面化学性质可调节、结构灵活性和比表面积高的特点；概括单层和多层MXene储氢的理论研究结果，强调过渡金属元素和表面官能团基团在优化氢吸附能力中的作用；总结MXene储氢的实验研究结果，展示其在液氮低温下和接近室温条件下储氢的潜力；理论预测与实验结果的比较分析强调了进一步实验验证和计算优化的必要性。【展望】 提出为了提升MXene储氢性能，应关注缺陷工程、层间距优化和机器学习辅助筛选，为推进MXene材料作为实用的氢储存解决方案奠定了基础。

关键词： 储氢材料； MXene； 密度泛函理论计算； 机器学习； 实验结果

Abstract

Significance Hydrogen energy is widely regarded as a promising clean and renewable energy source， but its practical application is hindered by challenges in efficient and secure storage. Among various hydrogen storage materials， MXene， a type of two-dimensional material， has attracted significant attention due to its adjustable surface chemical properties， structural flexibility， and high specific surface area. This study reviews both theoretical and experimental research on MXene materials for hydrogen storage and explores the factors influencing their storage performance.

Progress This paper first examines theoretical studies on hydrogen storage in single-layer and multi-layer MXene structures. Early theoretical research by Hu et al. （2013） used density functional theory （DFT） calculations to evaluate the hydrogen storage potential of Ti₂C， revealing a hydrogen storage capacity of up to 8.6 wt% under environmental conditions， meeting the target set by the US Department of Energy. In 2020， a study introduced a high-throughput screening method to identify promising hydrogen storage materials among two-dimensional nanostructures， pinpointing six ideal candidates， including C-based and B-based structures， with theoretical hydrogen weight densities exceeding 5.5 wt%. This method highlights the importance of balancing adsorption energy， thermodynamic stability， and electronic properties for effective hydrogen capture. A first-principles study in 2024 systematically analyzed how mixed and uniform surface functional groups affect the hydrogen adsorption and storage capacity of single-layer Ti₃C₂T_x. The study investigated various surface functional groups， including O， OH， F， and H， both individually and in combination， and evaluated their effects on hydrogen adsorption energy and capacity. Emphasis was placed on the role of transition metal elements and surface functional groups in optimizing hydrogen adsorption. Another study in 2024 utilized first-principles calculations to investigate the hydrogen adsorption behavior in multi-layer MXenes， with a focus on the effects of interlayer spacing and transition metal elements. The results indicated that interlayer spacing played a crucial role in regulating hydrogen adsorption behavior： a narrower spacing enhanced the adsorption of hydrogen molecules through Kubas-type interactions， while an expanded spacing facilitated the chemical adsorption of hydrogen atoms. At room temperature and 60 bar， multi-layer Ti₂C exhibited a hydrogen storage capacity as high as 8.8 wt%， with strong physical adsorption contributing to its excellent performance. These findings highlight the potential of interlayer spacing manipulation in optimizing hydrogen storage and release kinetics. Experimental studies have further demonstrated the potential of MXene for hydrogen storage under low liquid nitrogen temperatures and near-room-temperature conditions. A research report in 2024 indicated that multi-layer Ti₃C₂T_x achieved an excellent hydrogen storage capacity of approximately 10.47 wt% at 77 K and 25 bar. Additionally， Shui et al. （2012） prepared partially etched multilayer Ti₂CT_x， which achieved 8.8 wt% hydrogen absorption at 60 bar near room temperature. The high hydrogen storage capacity was attributed to the unique nano-pump effect promoted by the fluorine surface groups and a narrow interlayer spacing of approximately 7 Å.

Conclusions and Prospects Although theoretical studies have predicted various MXene materials with high hydrogen storage potential， only a limited number have been experimentally investigated. There is an urgent need for extensive experimental research to validate and identify MXene materials with excellent hydrogen storage capacities. Combining experimental studies with advanced computational approaches， such as machine learning and high-throughput screening， can accelerate the discovery process. Additionally， these techniques offer deeper insights into the relationship between material composition， structure， and storage performance， contributing to a better understanding of MXene hydrogen storage mechanisms. Although the theoretical composition of MXene is well understood， the synthesis process often introduces defects within the layers and on the surface， along with grafted functional groups. Previous studies show that defects and functional groups significantly affect the hydrogen storage capacity of MXene by altering the interaction between hydrogen molecules and MXene surfaces—either enhancing or inhibiting storage performance. Therefore， developing techniques to precisely control and tailor these defects and functional groups is essential for optimizing the hydrogen storage performance of MXene. One key advantage of multi-layer MXene is its ability to store substantial amounts of hydrogen at near-ambient temperatures. Compared to single-layer MXene， the hydrogen storage mechanism in multi-layer MXene is more complex， with interlayer spacing emerging as a key factor. Adjusting the interlayer spacing directly affects hydrogen adsorption energy， diffusion rate， and hydrogen storage kinetics. Controlling the interlayer spacing is a crucial strategy for enhancing the hydrogen storage performance of multi-layer MXene. Future research should prioritize developing precise methods for adjusting interlayer spacing， whether through chemical modification or external factors such as pressure and temperature. By optimizing the interlayer spacing， the hydrogen storage density and cycling stability of MXene can be significantly improved， making it highly viable for practical applications. Additionally， further studies are necessary to investigate the interactions between interlayer spacing and surface functional groups to understand how these factors collectively contribute to the overall hydrogen storage performance of multi-layer MXene.

Keywords： hydrogen storage materials； MXene； density functional theory calculations； machine learning； experimental results

参考文献（References）

［1］ GAO Y， LI Z L， WANG P， et al. Experimentally validated design principles of heteroatom-doped-graphene-supported calcium single-atom materials for non-dissociative chemisorption solid-state hydrogen storage ［J］. Nature Communications， 2024， 15（928）.

［2］ HU H Z， ZHANG X X， Li S S， et al. A review of body-centered cubic-structured alloys for hydrogen storage： composition， structure， and properties ［J］. Rare Metals， 2024.

［3］ ZOU R， LI J L， CUI J R， et al. Catalyst-free synthesis of lithium hydride at room temperature ［J］. Chemical Communications， 2023， 59（18）： 2660-2663.

［4］ ZHNG W J， CUI J R， WANG S S， et al. Deforming lanthanum trihydride for superionic conduction ［J］. Nature， 2023， 616（7955）： 73-76.

［5］ RIVARD E， TRUDEAU M， ZAGHIB K. Hydrogen storage for mobility： a review ［J］. Materials， 2019， 12（12）： 1973.

［6］ LIU S Y， SHUI J L. Mechanism and properties of emerging nanostructured hydrogen storage materials ［J］. Battery Energy， 2022， 1（4）： 20220033.

［7］ THIYAGARAJAN S R， EMADI H， HUSSAIN A， et al. A comprehensive review of the mechanisms and efficiency of underground hydrogen storage ［J］. Journal of Energy Storage， 2022， 51： 104490.

［8］ 张红兵， 李道火. 纳米储氢合金制备方法的研究进展［J］. 中国粉体技术， 2000， 6（6）： 21-25.

ZHANG H B， LI D H. Research development on fabrication methods of nanoscale hydrogen storage alloys［J］. China Powder Science and Technology， 2000， 6（6）： 21-25.

［9］ LIU S Y， LIU J Y， LIU X F， et al. Non-classical hydrogen storage mechanisms other than chemisorption and physisorption ［J］. Applied Physics Reviews， 2022， 9（2）： 021315.

［10］ LIU S Y， ZHANG Y， ZHU F Z， et al. Mg‐MOF‐74 derived defective framework for hydrogen storage at above‐ambient temperature assisted by Pt catalyst ［J］. Advanced Science， 2024， 11（18）： 2401868.

［11］ NIVEDHITHA K S， BEENA T， BANAPURMATH N R， et al. Advances in hydrogen storage with metal hydrides： mechanisms， materials， and challenges ［J］. International Journal of Hydrogen Energy， 2024， 61：1259-1273.

［12］ PANG Y， WAN X， LI Y C， et al. Evolution of nitrogen‐coordinated metal single atoms toward single‐atom alloys on MgH₂ as efficient and stable hydrogen spillover catalysts ［J］. Advanced Materials， 2024， 36（50）： 2412942.

［13］ LI Z Y， LIU S Y， PU Y H， et al. Single-crystal ZrCo nanoparticle for advanced hydrogen and H-isotope storage ［J］. Nature Communications， 2023， 14（7966）.

［14］ ALLENDORF M D， STAVILA V， SNIDER J L， et al. Challenges to developing materials for the transport and storage of hydrogen ［J］. Nature Chemistry， 2022， 14（11）： 1214-1223.

［15］ 周超， 王辉， 欧阳柳章， 等. 高压复合储氢罐用储氢材料的研究进展［J］. 材料导报， 2019， 33（1）： 117126.

ZHOU C， WANG H， OUYANG L Z， et al. The state of the art of hydrogen storage materials for high-pressure

hybrid hydrogen vessel ［J］. Materials reports， 2019， 33（1）： 117126.

［16］ OH H， TUMANOV N， BAN V R Y， et al. Small-pore hydridic frameworks store densely packed hydrogen ［J］. Nature Chemistry， 2024， 16（5）： 809-816.

［17］ ZHENG J Y， LIU X X， XU P， et al. Development of high pressure gaseous hydrogen storage technologies ［J］. International Journal of Hydrogen Energy， 2012， 37（1）： 1048-1057.

［18］ ALZOHBI G， ALMOAIKEL A， ALSHUHAIL L. An overview on the technologies used to store hydrogen ［J］. Energy Reports， 2023， 9： 28-34.

［19］ LIU Y N， GAO H G， ZHU Y F， et al. Excellent catalytic activity of a two-dimensional Nb₄C₃T_x （MXene） on hydrogen storage of MgH₂ ［J］. Applied Surface Science， 2019， 493： 431-440.

［20］ HUANG Z N， WANG Y Q， ZHANG M G. Excellent catalytic activity of two-dimensional Ti₂C and Ti₂CT₂ （T=O， F， OH） monolayers on hydrogen storage of MgH₂： first-principles calculations ［J］. International Journal of Hydrogen Energy， 2021， 46（66）： 33176-33185.

［21］ KUMAR P， SINGH S， HASHMI S A R， et al. MXenes： emerging 2D materials for hydrogen storage ［J］. Nano Energy， 2021， 85： 105989.

［22］ LIM K R G， SHEKHIREV M， WYATT B C， et al. Fundamentals of MXene synthesis ［J］. Nature Synthesis， 2022， 1（8）： 601-614.

［23］ ZHANG J， WANG W， CHEN X， et al. Single-atom Ni supported on TiO₂ for catalyzing hydrogen storage in MgH₂ ［J］. Journal of the American Chemical Society， 2024， 146（15）： 10432-10442.

［24］ XU N， WANG K， ZHU Y， et al. PdNi biatomic clusters from metallene unlock record-low onset dehydrogenation temperature for bulk-MgH₂ ［J］. Advanced Materials， 2023， 35（38）： 2303173.

［25］ LAN Z， FU H， ZHAO R， et al. Roles of in situ-formed NbN and Nb₂O₅ from N-doped Nb₂C MXene in regulating the re/hydrogenation and cycling performance of magnesium hydride ［J］. Chemical Engineering Journal， 2022， 431： 133985.

［26］ LIU H Z， DUAN X Q， WU Z Y， et al. Exfoliation of compact layered Ti₂VAlC₂ MAX to open layered Ti₂VC₂ MXene towards enhancing the hydrogen storage properties of MgH₂ ［J］. Chemical Engineering Journal， 2023， 468： 143688.

［27］ ZHOU D S， ZHAO D L， SUN H F， et al. Two-dimensional material MXene and its derivatives enhance the hydrogen storage properties of MgH₂： a review and summary ［J］. International Journal of Hydrogen Energy， 2024， 71： 279-297.

［28］ 张秋雨， 杜四川， 马哲文， 等. 镁基储氢材料的研究进展［J］. 科学通报， 2022， 67（19）： 21582171.

ZHANG Q Y， DU S C， MA Z W， et al. Recent advances in Mg-based hydrogen storage materials ［J］. Chinese science bulletin， 2022， 67（19）： 21582171.

［29］ ZHAO Y Y， WANG B L， REN L， et al. Nanostructured MXene-based materials for boosting hydrogen sorption properties of Mg/MgH₂ ［J］. Materials Reports： Energy， 2024， 4（1）： 100255.

［30］ XIA A， ZHENG J G， ZANG Q B， et al. Facile construction of MXene-supported niobium hydride nanoparticles toward reversible hydrogen storage in magnesium borohydride ［J］. Rare Metals， 2024， 43（9）： 4387-4400.

［31］ YUAN Z L， ZHANG D F， FAN G X， et al. N-doped carbon coated Ti₃C₂ MXene as a high-efficiency catalyst for improving hydrogen storage kinetics and stability of NaAlH₄ ［J］. Renewable Energy， 2022， 188： 778-787.

［32］ LIU S Y， LIU J Y， LIU X F， et al. Hydrogen storage in incompletely etched multilayer Ti₂CT_x at room temperature ［J］. Nature Nanotechnology， 2021， 16（3）： 331-336.

［33］ ANASORI B， LUKATSKAYA M R， GOGOTSI Y. 2D metal carbides and nitrides （MXenes） for energy storage ［J］. Nature Reviews Materials， 2017， 2（16098）.

［34］ XU J， ZHAO M Q， WANG Y， et al. Demonstration of Li-ion capacity of MAX phases ［J］. ACS Energy Letters 2016， 1（6）： 1094-1099.

［35］ NAGUIB M， KURTOGLU M， PRESSER V， et al. Two-dimensional nanocrystals produced by exfoliation of Ti₃AlC₂ ［J］. Advanced Materials， 2011， 23（37）： 4248-4253.

［36］ LI K， LIANG M Y， WANG H， et al. 3D MXene architectures for efficient energy storage and conversion ［J］. Advanced Functional Materials， 2020， 30（47）： 2000842.

［37］ ZHANG J Q， ZHAO Y F， GUO X， et al. Single platinum atoms immobilized on an MXene as an efficient catalyst for the hydrogen evolution reaction ［J］. Nature Catalysis， 2018， 1（12）： 985-992.

［38］ YU Y H， YI P， XU W B， et al. Environmentally tough and stretchable MXene organohydrogel with exceptionally enhanced electromagnetic interference shielding performances ［J］. Nano-Micro Letters， 2022， 14（77）.

［39］ CHEN G， ZHANG Y， CHENG H H， et al. Effects of two-dimension MXene Ti₃C₂ on hydrogen storage performances of MgH₂-LiAlH₄ composite ［J］. Chemical Physics， 2019， 522： 178-187.

［40］ XIAN K C， GAO M X， LI Z L， et al. Superior kinetic and cyclic performance of a 2D titanium carbide incorporated 2LiH+MgB₂ composite towards highly reversible hydrogen storage ［J］. ACS Applied Energy Materials， 2019， 2（7）： 4853-4864.

［41］ HU Q K， SUN D D， WU Q H， et al. MXene： a new family of promising hydrogen storage medium ［J］. The Journal of Physical Chemistry A， 2013， 117（51）： 14253-14260.

［42］ HU Q K， WANG H Y， WU Q H， et al. Two-dimensional Sc₂C： a reversible and high-capacity hydrogen storage material predicted by first-principles calculations ［J］. International Journal of Hydrogen Energy， 2014， 39（20）：10606-10612.

［43］ WANG S， DU Y L， LIAO W H， et al. Hydrogen adsorption， dissociation and diffusion on two-dimensional Ti₂C monolayer ［J］. International Journal of Hydrogen Energy， 2017， 42（44）： 27214-27219.

［44］ WANG C， TANG C M， FU L. An effective method to screen carbon （boron， nitrogen） based two-dimensional hydrogen storage materials ［J］. International Journal of Hydrogen Energy， 2020， 45（46）： 25054-25064.

［45］ CHU Y Z， LAU K C. First-principles study of hydrogen storage application of Ti₃C₂T_x monolayer MXene ［J］. International Journal of Hydrogen Energy， 2024， 57： 1144-1151.

［46］ ZHENG B， LI J X， WANG L L， et al. Hydrogen storage in MXenes： controlled adjustment of sorption by interlayer distance and transition metal elements ［J］. International Journal of Hydrogen Energy， 2024， 50： 1555-1561.

［47］ SAHARAN S， GHANEKAR U， MEENA S. V₂N MXene for hydrogen storage： first-principles calculations ［J］. The Journal of Physical Chemistry C， 2024， 128（4）： 1612-1620.

［48］ GHOTIA S， KUMAR A， SUDARSAN V， et al. Multilayered Ti₃C₂T_x MXenes： a prominent material for hydrogen storage ［J］. International Journal of Hydrogen Energy， 2024， 52： 100-107.

［49］ PATCHKOVSKII S， TSE J S， YURCHENKOR S N， et al. Graphene nanostructures as tunable storage media for molecular hydrogen ［J］. Proceedings of the National Academy of Sciences of the United States of America， 2005， 102（30）： 10439-10444.

［50］ OSTI N C， NAGUIB M， TYAGI M， et al. Evidence of molecular hydrogen trapped in two-dimensional layered titanium carbide-based MXene ［J］. Physical Review Materials， 2017， 1（2）： 024004.

［51］ CHENG J W， LI T W， WANG Y Y， et al. High-throughput screening of MXenes for hydrogen storage via graph neural network ［J］. Applied Surface Science， 2023， 641： 158560.