Atomic interface engineering of ultra-small metastable α-MoC1-x enables electronically modulated Pt catalysts for hydrogen evolution
image: Highly dispersed ultra-small pure-phase α-MoC1-x is constructed to realize atomic-level interface configuration that enables the preferential anchoring of Pt atoms onto the metastable α-MoC1-x phase through strong metal-support interactions, which significantly improves the atomic utilization efficiency of Pt in hydrogen evolution reaction.
Credit: Plasma Catalysis laboratory, Dalian University of Technology
The rational design of platinum-based electrocatalysts with optimized metal-support electronic interactions remains a fundamental challenge in achieving atom-efficient hydrogen evolution reaction (HER). This study demonstrates a coordination-driven synthesis strategy to engineer highly dispersed ultra-small α-MoC1-x anchored on nitrogen-doped carbon frameworks (NC), leveraging the unique metal-organic coordination chemistry between molybdenum species and imidazolate ligands in ZIF-8 precursors. Through precise control of the carbide crystallization process, we establish an atomic-level interface configuration that enables the preferential anchoring of Pt atoms onto the metastable α-MoC1-x phase. The resulting strong metal-support interaction (SMSI) induces significant electron redistribution at the Pt/α-MoC1-x interface, as evidenced by X-ray absorption spectroscopy (XAS). The optimized Pt/α-MoC1-x/NC architecture demonstrates exceptional HER performance with low overpotentials of 19 and 84 mV at current density of 10 and 100 mA cm-2. Remarkably, it achieves a mass activity of 15.3 A mgPt-1 at 100 mV overpotential, 10.9-fold enhancement compared to commercial 20% Pt/C (1.4 A mgPt-1). This work establishes a new paradigm for constructing interfacial electronic environments through support dispersion engineering, providing fundamental insights into the design principles of high-efficiency catalysts for sustainable hydrogen production.
The urgent need to decarbonize global energy systems has positioned hydrogen as a pivotal clean energy carrier, offering carbon-neutral combustion products and compatibility with renewable energy storage. Among hydrogen production technologies, electrochemical water decomposition stands out as an efficient and sustainable technology to produce hydrogen. It is crucial to design hydrogen evolution reaction (HER) catalysts with quick reaction kinetics and low overpotentials that trigger proton reduction. So far, Pt-based catalysts remain the benchmark HER catalysts despite facing critical limitations inherent scarcity and high cost, necessitating atomic-level utilization optimization through innovative structural engineering. A tremendous number of metallic catalysts have demonstrated that surface and interface engineering can profoundly alter electronic configurations of active sites, thereby regulating the adsorption-desorption behaviors of reactants, intermediates, and products, thereby improving the catalytic reactivity.
A team of material scientists led by Chuan Shi from Dalian University of Technology in Dalian, China recently developed a coordination confinement strategy employing ZIF-8-derived nitrogen-doped carbon (NC) frameworks to stabilize highly dispersed ultra-small metastable α-MoC1-x (~2.3 nm). The imidazolate ligands in ZIF-8 precursors selectively coordinate with Mo species, enabling controlled carbide crystallization during pyrolysis while suppressing phase transformation. Subsequent high-temperature activation induces spontaneous anchoring of Pt atoms onto α-MoC1-x surfaces through interfacial electronic interactions, as confirmed through AC HAADF-STEM imaging and XAFS spectroscopy. This enhancement is attributed to the synergistic effect between α-MoC1-x and NC, which results in a higher utilization efficiency of Pt atoms. Additionally, DFT calculations demonstrate that the distinctive interface created by the introduction of α-MoC1-x induces charge redistribution, lowering the water dissociation energy barrier and optimizing hydrogen adsorption free energy. This work establishes a universal platform for engineering metastable carbide phases with atomic-level metal dispersion, providing fundamental insights into interface-dominated electrocatalysis.
The team published their research paper in Nano Research on September 2, 2025.
“In this work, we present a novel interfacial engineering approach that successfully synthesizes pure-phase and highly dispersed α-MoC1-x nanoparticles, which are effectively dispersed on a carbon carrier. This highly dispersed molybdenum carbide serves as a robust support for Pt, facilitating improved dispersion and interaction between Pt and α-MoC1-x,” said Chuan Shi, corresponding author of the research paper, professor in the State Key Laboratory of Fine Chemicals and School of Chemistry at Dalian University of Technology. Dr. Shi is also the Yangtze River Scholar Professor of Chinese Ministry of Education.
“This work not only underscores the potential of strong metal-support interactions in catalyst design but also provides critical insights for the development of highly efficient, low-Pt loading electrocatalysts.” said Chuan Shi.
Other contributors include Long Xiao, Bingbing Chen, Peiyuan Mao, Wenqian Xu, Manyi Yang from State Key Laboratory of Fine Chemicals and School of Chemistry at Dalian University of Technology in Dalian, China; and Huizhu Cai from the College of Chemistry and Environmental Engineering at ShenZhen University, and Rui Gao from the School of Chemistry and Chemical Engineering at Inner Mongolia University.
This work was financially supported by the National Key R & D Program of China No. 2021YFA1501102, the National Natural Science Foundation of China (No. 22276023, 22472019, 22409133, 22172083), the Fundamental Research Funds for the Central Universities (DUT22LAB602), Liaoning Binhai Laboratory Project (LBLF-202306).
About Nano Research
Nano Research is a peer-reviewed, open access, international and interdisciplinary research journal, sponsored by Tsinghua University and the Chinese Chemical Society, published by Tsinghua University Press on the platform SciOpen. It publishes original high-quality research and significant review articles on all aspects of nanoscience and nanotechnology, ranging from basic aspects of the science of nanoscale materials to practical applications of such materials. After 18 years of development, it has become one of the most influential academic journals in the nano field. Nano Research has published more than 1,000 papers every year from 2022, with its cumulative count surpassing 7,000 articles. In 2024 InCites Journal Citation Reports, its 2024 IF is 9.0 (8.7, 5 years), and it continues to be the Q1 area among the four subject classifications. Nano Research Award, established by Nano Research together with TUP and Springer Nature in 2013, and Nano Research Young Innovators (NR45) Awards, established by Nano Research in 2018, have become international academic awards with global influence.