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Amorphous Molybdenum Phosphide Nanoparticles for Electrocatalytic Hydrogen Evolution

McEnaney, Joshua M. and Crompton, J. Chance and Callejas, Juan F. and Popczun, Eric J. and Biacchi, Adam J. and Lewis, Nathan S. and Schaak, Raymond E. (2014) Amorphous Molybdenum Phosphide Nanoparticles for Electrocatalytic Hydrogen Evolution. Chemistry of Materials, 26 (16). pp. 4826-4831. ISSN 0897-4756. http://resolver.caltech.edu/CaltechAUTHORS:20140930-095609063

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Abstract

Amorphous molybdenum phosphide (MoP) nanoparticles have been synthesized and characterized as electrocatalysts for the hydrogen-evolution reaction (HER) in 0.50 M H_2SO_4 (pH 0.3). Amorphous MoP nanoparticles (having diameters of 4.2 ± 0.5 nm) formed upon heating Mo(CO)6 and trioctylphosphine in squalane at 320 °C, and the nanoparticles remained amorphous after heating at 450 °C in H_2(5%)/Ar(95%) to remove the surface ligands. At mass loadings of 1 mg cm^–2, MoP/Ti electrodes exhibited overpotentials of −90 and −105 mV (−110 and −140 mV without iR correction) at current densities of −10 and −20 mA cm^–2, respectively. These HER overpotentials remained nearly constant over 500 cyclic voltammetric sweeps and 18 h of galvanostatic testing, indicating stability in acidic media under operating conditions. Amorphous MoP nanoparticles are therefore among the most active known molybdenum-based HER systems and are part of a growing family of active, acid-stable, non-noble-metal HER catalysts.


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http://dx.doi.org/10.1021/cm502035sDOIArticle
http://pubs.acs.org/doi/abs/10.1021/cm502035sPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/cm502035sPublisherSupporting Information
Additional Information:© 2014 American Chemical Society. Received: June 4, 2014; revised: July 15, 2014; published: July 17, 2014. This work was supported at PSU by the National Science Foundation (NSF) Center for Chemical Innovation on Solar Fuels (CHE-1305124) and at Caltech by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award DE-SC0004993. TEM imaging was performed in the Penn State Microscopy and Cytometry Facility (University Park, PA) and HRTEM imaging, EDS spectra, XPS spectra, and DRIFTS spectra were acquired at the Materials Characterization Laboratory of the Penn State Materials Research Institute. J.M.M. thanks Jennifer Gray for assistance with analyzing the XPS spectra and Dr. Thomas Gordon for assistance with quantitative yield experiments.
Group:CCI Solar Fuels
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Funding AgencyGrant Number
NSFCHE-1305124
Department of Energy (DOE)DE-SC0004993
Record Number:CaltechAUTHORS:20140930-095609063
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20140930-095609063
Official Citation:Amorphous Molybdenum Phosphide Nanoparticles for Electrocatalytic Hydrogen Evolution Joshua M. McEnaney, J. Chance Crompton, Juan F. Callejas, Eric J. Popczun, Adam J. Biacchi, Nathan S. Lewis, and Raymond E. Schaak Chemistry of Materials 2014 26 (16), 4826-4831
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:50117
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:02 Oct 2014 20:00
Last Modified:15 Dec 2014 19:11

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