The emerging molybdenum disulfide (MoS2) offers intriguing possibilities for realizing a transformative new catalyst for driving the hydrogen evolution reaction (HER). However, the trade-off between catalytic activity and long-term stability represents a formidable challenge and has not been extensively addressed. This study reports that metastable and temperature-sensitive chemically exfoliated MoS2 (ce-MoS2) can be made into electrochemically stable (5000 cycles), and thermally robust (300 °C) while maintaining synthetic scalability and excellent catalytic activity through physical-transformation into 3D structurally deformed nanostructures. The dimensional transition enabled by a high throughput electrohydrodynamic process provides highly accessible, and electrochemically active surface area and facilitates efficient transport across various interfaces. Meanwhile, the hierarchically strained morphology is found to improve electronic coupling between active sites and current collecting substrates without the need for selective engineering the electronically heterogeneous interfaces. Specifically, the synergistic combination of high strain load stemmed from capillarity-induced-self-crumpling and sulfur (S) vacancies intrinsic to chemical exfoliation enables simultaneous modulation of active site density and intrinsic HER activity regardless of continuous operation or elevated temperature. These results provide new insights into how catalytic activity, electrochemical-, and thermal stability can be concurrently enhanced through the physical transformation that is reminiscent of nature, in which properties of biological materials emerge from evolved dimensional transitions.
|Original language||English (US)|
|State||Published - Nov 27 2017|
Bibliographical noteFunding Information:
Y.-C.C. and A.-Y.L. contributed equally to this work. V.T. gratefully acknowledges the research award from the Doctoral New Investigator Award from ACS Petroleum Fund (ACS PRF 54717-DNI10, V.T.). Characterization and fabrication of HER electrodes in this work were performed as User Proposals (#4240) at the Molecular Foundry, Lawrence Berkeley National Lab, supported by the Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. Raman spectroscopy was performed at the Joint Center for Artificial Photosynthesis (JCAP), a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. Y.C. acknowledges the fellowship support from National Aeronautics and Space Administration (NASA) grant no. NNX15AQ01. Work at Sandia, including experimental design, materials synthesis, microscopy, were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering. Equipment at Sandia were furnished with support from the Laboratory Directed Research and Development programs. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA-0003525. A.Y.L, X.Y., and L.J.L. acknowledge the support from KAUST. V.T. is indebted to Dr. Hidetaka Ishihara, Xuan Wei, Jose Hernandez, Teresa L. Chen, and Vipawee Limsakoune, for the fruitful discussion in droplet dynamics and assistance in instrumentation. Note: The spelling of the first name of the author Bryan Kaehr was corrected on November 21, 2017, after initial publication online.
© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
- bioinspired dimensional transitions
- hydrogen evolution reactions
- molybdenum disulfide
ASJC Scopus subject areas
- Materials Science(all)
- Mechanics of Materials
- Mechanical Engineering