Identifying Catalytic Active Sites of Trimolybdenum Phosphide (Mo3P) for Electrochemical Hydrogen Evolution

Kondori, Alireza; Esmaeilirad, Mohammadreza; Baskin, Artem; Song, Boao; Wei, Jialiang; Chen, Wei; Segre, Carlo U.; Shahbazian‐Yassar, Reza; Prendergast, David; Asadi, Mohammad

doi:10.1002/aenm.201900516

Title: Identifying Catalytic Active Sites of Trimolybdenum Phosphide (Mo₃P) for Electrochemical Hydrogen Evolution

Journal Article · Thu May 02 00:00:00 EDT 2019 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.201900516· OSTI ID:1531000

^[1]; Esmaeilirad, Mohammadreza ^[1]; Baskin, Artem ^[2]; Song, Boao ^[3]; Wei, Jialiang ^[1]; Chen, Wei ^[1]; Segre, Carlo U. ^[1]; Shahbazian‐Yassar, Reza ^[3]; Prendergast, David ^[2];

^[1]

Illinois Institute of Technology, Chicago, IL (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Department of Mechanical and Industrial Engineering, Chicago, IL (United States)

Abstract Solid‐state electrocatalysis plays a crucial role in the development of renewable energy to reshape current and future energy needs. However, finding an inexpensive and highly active catalyst to replace precious metals remains a big challenge for this technology. Here, tri‐molybdenum phosphide (Mo ₃ P) is found as a promising nonprecious metal and earth‐abundant candidate with outstanding catalytic properties that can be used for electrocatalytic processes. The catalytic performance of Mo ₃ P nanoparticles is tested in the hydrogen evolution reaction (HER). The results indicate an onset potential of as low as 21 mV, H ₂ formation rate, and exchange current density of 214.7 µmol s ⁻¹ g ⁻¹ _cat (at only 100 mV overpotential) and 279.07 µA cm ⁻² , respectively, which are among the closest values yet observed to platinum. Combined atomic‐scale characterizations and computational studies confirm that high density of molybdenum (Mo) active sites at the surface with superior intrinsic electronic properties are mainly responsible for the remarkable HER performance. The density functional theory calculation results also confirm that the exceptional performance of Mo ₃ P is due to neutral Gibbs free energy (Δ G _H* ) of the hydrogen (H) adsorption at above 1/2 monolayer (ML) coverage of the (110) surface, exceeding the performance of existing non‐noble metal catalysts for HER.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; DMR-1420709; ECCS-1542205; JEM-ARM200CF; DMR-0959470; DMR-1720139; DEAC02‐05CH11231

OSTI ID:: 1531000

Alternate ID(s):: OSTI ID: 1510349

Journal Information:: Advanced Energy Materials, Vol. 9, Issue 22; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 35 works

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25 ENERGY STORAGE
Solid-state electrocatalysis
Tri-molybdenum phosphide
Non-precious metals
Active sites
Hydrogen evolution reaction

Title: Identifying Catalytic Active Sites of Trimolybdenum Phosphide (Mo3P) for Electrochemical Hydrogen Evolution

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Title: Identifying Catalytic Active Sites of Trimolybdenum Phosphide (Mo₃P) for Electrochemical Hydrogen Evolution