High-Entropy MXenes as Next-Generation Electrocatalysts for Efficient and Durable Hydrogen Evolution

Irshad Ahmad Mir; Shakeel Ahmed; Muhammad Naveed Afridi; Waqas Saeed; Baoji Miao; Sachin Kumar; Mohammed A. Al-Tahan; Jinbo Bai; Muhammad Asad; Surjyakanta Rana

doi:10.1007/s12209-026-00484-2

Transactions of Tianjin University ›› :1 -11. DOI: 10.1007/s12209-026-00484-2

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High-Entropy MXenes as Next-Generation Electrocatalysts for Efficient and Durable Hydrogen Evolution

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¹Henan International Joint Laboratory of Nano-Photoelectric Magnetic Material, School of Materials Science and Engineering, Henan University of Technology, 450001, Zhengzhou, China

²Interdisciplinary Research Center for Hydrogen Technologies and Carbon, King Fahd University of Petroleum & Minerals, 31261, Dhahran, Saudi Arabia

³School of Mechanical and Electrical Engineering, Henan University of Technology, 450001, Zhengzhou, China

⁴Department of Applied Science and Humanities, ITS, Engineering College, 201310, Greater Noida, India

⁵LMPS-Laboratoire de Mécanique Paris-Saclay, CNRS, Université Paris-Saclay, Centrale Supélec, ENS Paris-Saclay, 91190, Gif-Sur-Yvette, France

⁶Department of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5, 616628, Prague, Czech Republic

⁷Centre for Functional and Surface Functionalized Glass, Alexander Dubček University of Trenčín, 911 50, Trenčín, Slovakia

^a mbjhaut@163.com

^b asadm@vscht.cz

^c surjyakanta.rana@tnuni.sk

Irshad Ahmad Mir

Irshad Ahmad Mir received his Ph.D. degree from the School of Physical Sciences, Jawaharlal Nehru University (JNU), New Delhi, India, in 2018. He subsequently pursued postdoctoral research at Shenzhen University, China, from 2019 to 2021. He is currently working as a postdoctoral researcher at the School of Materials Science and Engineering, Henan University of Technology, Zhengzhou, China. His research expertise encompasses the synthesis and structural characterization of a wide range of advanced nanomaterials, including multi-element core/shell quantum dots (QDs), high-entropy MAX phases and MXenes, metal oxides, metal sulfides, metal–organic frameworks (MOFs), and various hybrid architectures such as 2D/0D, 2D/1D, and 2D/2D composites. His research interests focus on the application of these nanomaterials in biosensing, metal ion sensing, nano-bio interactions, photocatalysis, electrocatalysis for water splitting (particularly the hydrogen evolution reaction, HER), gas sensing, and photo-electrocatalysis. He brings a unique combination of expertise in both zero-dimensional quantum dots and two-dimensional high-entropy layered materials, positioning him to develop next-generation heterostructure catalysts for sustainable energy and environmental applications .

Baoji Miao

Baoji Miao received his Ph.D. degree in Physical Chemistry from the University of Bourgogne, France, in 2008, under a French government scholarship, followed by postdoctoral training at the French Atomic Energy Commission (CEA Saclay) from 2008 to 2010, working under the supervision of Dr. Nathalie Herlin-Boime on the laser pyrolysis synthesis of functional nanomaterials. He obtained his Master’s degree in Materials Science and Engineering from INP Toulouse (ENSIACET), France, in 2004, and his Bachelor’s degree from Beihang University, China, in 2002. He is currently a Professor and the Vice Dean of the School of Materials Science and Engineering at Henan University of Technology, where he also serves as the Director of the Henan International Joint Laboratory of Nano-Photoelectromagnetic Materials. His research interests include the synthesis and structural characterization of inorganic nanomaterials, with a focus on MAX phases, MXenes, TiO₂, ZrO₂, MoS₂, quantum dots, and their composites for applications in electrocatalysis (HER, NRR), photocatalysis, electromagnetic wave absorption, and energy storage. He has published over 30 peer-reviewed papers in high-impact journals, including Renewable and Sustainable Energy Reviews, Advanced Composites and Hybrid Materials, Journal of Colloid and Interface Science, and Ceramics International. He holds nine authorized patents and has received several awards, including the Henan Provincial Science and Technology Progress Award (Third Class, 2023) and the Henan Provincial Department of Education Science and Technology Achievement Award (Second Class, 2022). He has led multiple provincial and national research projects, including the Henan International Joint Laboratory for Nano-Photoelectromagnetic Materials. His recent work concentrates on high-entropy MXene/doped MoS₂ composites and QD/2D heterostructures for sustainable energy conversion applications .

Muhammad Asad

Muhammad Asad joined the Sofer Group as a CHEMFELLS VII Fellow in April 2025. He received his Master’s degree in Chemistry from Bahauddin Zakariya University, Multan, Pakistan, in 2018, and earned his Ph.D. in Inorganic Chemistry from Zhengzhou University, Henan, China, in 2022. From 2022 to 2024, he worked as a Postdoctoral Researcher at Henan University of Technology, China. His research focuses on the design and synthesis of luminescent porous materials, including metal–organic frameworks (MOFs), covalent organic frameworks (COFs), and covalent organic polymers (COPs), as well as two-dimensional (2D) materials such as MXenes, metal oxides, and metal sulfides. His work explores their applications in luminescent sensing and electrocatalysis, with an emphasis on sustainable environmental and energy technologies .

Surjyakanta Rana

Surjyakanta Rana is a Senior Researcher at the Department of Functional Materials, FUNGLASS, Alexander Dubček University of Trenčín, Slovakia, since 2021. He was a recipient of the prestigious Marie Skłodowska-Curie Fellowship in 2019. He has extensive experience in the development, modification, and advanced characterization of functional materials, with a strong focus on catalytic materials, nanomaterials, and heterogeneous catalysis. His research contributions span a broad range of advanced material systems, including graphene-based nanocomposites, metal–organic frameworks (MOFs), mesoporous silica, Zirconia, Titania, various cationic and anionic clays (montmorillonite and layered double hydroxides), MXenes, and 3D-printed ceramic scaffolds. He has successfully applied these materials in key areas such as photocatalysis, gas separation, and fine chemical synthesis, addressing critical challenges in sustainable energy and environmental remediation. Dr. Rana has established a strong publication record in peer-reviewed international journals and has actively contributed to collaborative research projects at both national and international levels. His work is recognized for advancing the design of efficient and environmentally friendly catalytic systems. In addition to his research achievements, he is involved in mentoring students and early-career researchers, supporting the development of future scientists in the field of materials science .

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Abstract

In this study, we systematically investigated the role of configurational entropy and morphological control in enhancing the electrocatalytic performance of MXenes for the hydrogen evolution reaction (HER). We successfully synthesized a series of MAX phase precursors with increasing entropy: low-entropy (single-metal) Ti₂AlC, V₂AlC, Nb₂AlC; a medium-entropy solid solution (Ti₁/₃V₁/₃Nb₁/₃)₂AlC; and a high-entropy (Ti₁/₄V₁/₄Nb₁/₄Ta₁/₄)₂AlC. X-ray diffraction analysis confirmed the successful formation of layered hexagonal MAX phases and their transformation into MXenes, with characteristic shifts in the (002) reflection indicating interlayer expansion. Scanning and transmission electron microscopies reveal the evolution from dense, plate-like MAX grains to exfoliated, accordion-like multilayered Ti₁/₂V₁/₂Nb₁/₂Ta₁/₂CT_z MXene and sheets with few-layered morphologies, while X-ray photoelectron spectroscopy demonstrates Al removal and the presence of mixed oxidation states for Ti, V, Nb, and Ta. The electrochemical analysis of HER revealed a clear trend of improved activity with increasing entropy. Single-metal MXenes exhibited overpotentials (η@10 mA/cm²) of 231–207 mV and Tafel slopes of 163–155 mV/dec. The medium-entropy (Ti₁/₃V₁/₃Nb₁/₃)₂CT_z MXene demonstrated enhanced performance (η ≈ 140 mV, Tafel slope ≈ 134 mV/dec), which was further surpassed by the high-entropy (multilayered) M-(Ti₁/₄V₁/₄Nb₁/₄Ta₁/₄)₂CT_z MXene (η ≈ 97 mV, Tafel slope ≈ 115 mV/dec). Exfoliating the high-entropy MXene into few-layered F- (Ti₁/₄V₁/₄Nb₁/₄Ta₁/₄)₂CT_z (F-Mxene) nanosheets yielded a tremendous enhancement, achieving an exceptional overpotential of 67 mV and a Tafel slope of 69 mV/dec. Alongside this superior activity, the high-entropy F-MXenes demonstrated tremendous electrochemical stability under prolonged operation, maintaining their performance for more than 55 h of continuous use. This combination of record-low overpotential, favorable kinetics, and robust durability establishes these compositionally complex, few-layered MXenes as a promising next-generation catalyst platform, paving the way for their application in efficient and sustainable hydrogen production systems.

Keywords

MAX Phases / High-Entropy MXenes / Electrocatalysis / Tafel slope / Overpotential / Stability and durability

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Irshad Ahmad Mir, Shakeel Ahmed, Muhammad Naveed Afridi, Waqas Saeed, Baoji Miao, Sachin Kumar, Mohammed A. Al-Tahan, Jinbo Bai, Muhammad Asad, Surjyakanta Rana. High-Entropy MXenes as Next-Generation Electrocatalysts for Efficient and Durable Hydrogen Evolution. Transactions of Tianjin University 1-11 DOI:10.1007/s12209-026-00484-2

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