Basal Plane Hydrogen Evolution Activity from Mixed Metal Nitride MXenes Measured by Scanning Electrochemical Microscopy

Journal Article · Tue May 19 00:00:00 EDT 2020 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.202001136· OSTI ID:1660008

Djire, Abdoulaye ^[1]; Wang, Xiang ^[2]; Xiao, Chuanxiao ^[3]; Nwamba, O. Charles ^[1]; Mirkin, Michael V. ^[2]; Neale, Nathan R. ^[1]

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1. National Renewable Energy Lab. (NREL), Golden, CO (United States). Chemistry and Nanoscience Center
2. City Univ. of New York (CUNY), NY (United States). Queens College
3. National Renewable Energy Lab. (NREL), Golden, CO (United States). Materials Science Center

2D early transition metal carbide and nitride MXenes have intriguing properties for electrochemical energy storage and electrocatalysis. These properties can be manipulated by modifying the basal plane chemistry. Here, mixed transition metal nitride MXenes, M-Ti₄N₃T_x (M = V, Cr, Mo, or Mn; T_x = O and/or OH), are developed by modifying pristine exfoliated Ti₄N₃T_x MXene with V, Cr, Mo, and Mn salts using a simple solution-based method. The resulting mixed transition metal nitride MXenes contain 6–51% metal loading (cf. Ti) that exhibit rich electrochemistry including highly tunable hydrogen evolution reaction (HER) electrocatalytic activity in a 0.5 m H₂SO₄ electrolyte as follows: V-Ti₄N₃T_x > Cr-Ti₄N₃T_x > Mo-Ti₄N₃T_x > Mn-Ti₄N₃T_x > pristine Ti₄N₃T_x with overpotentials as low as 330 mV at -10 mA cm^-2 with a charge-transfer resistance of 70 O. Scanning electrochemical microscopy (SECM) reveals the electrochemical activity of individual MXene flakes. The SECM data corroborate the bulk HER activity trend for M-Ti₄N₃T_x as well as provide the first experimental evidence that HER results from catalysis on the MXene basal plane. These electrocatalytic results demonstrate a new pathway to tune the electrochemical properties of MXenes for water splitting and related electrochemical applications.

• Research Organization: National Renewable Energy Laboratory (NREL), Golden, CO (United States)
• Sponsoring Organization: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
• Grant/Contract Number: AC36-08GO28308
• OSTI ID: 1660008
• Alternate ID(s): OSTI ID: 1630175
• Report Number(s): NREL/JA-5900-76684; MainId:9345; UUID:53da046e-2106-4534-9859-c8af6d027682; MainAdminID:13760
• Journal Information: Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 47 Vol. 30; ISSN 1616-301X
• Publisher: Wiley
• Country of Publication: United States
• Language: English

Related Subjects

2D materials
36 MATERIALS SCIENCE
basal plane
hydrogen evolution reaction
nitride MXenes
scanning electrochemical microscopy
solar-photochemistry