Intermetallic Single-Atom Alloy In–Pd Bimetallene for Neutral Electrosynthesis of Ammonia from Nitrate

Xie, Minghao; Tang, Sishuang; Li, Zhao; Wang, Maoyu; Jin, Zhaoyu; Li, Panpan; Zhan, Xun; Zhou, Hua; Yu, Guihua

doi:10.1021/jacs.3c03432

Intermetallic Single-Atom Alloy In–Pd Bimetallene for Neutral Electrosynthesis of Ammonia from Nitrate

Journal Article · Mon Jun 19 00:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c03432· OSTI ID:2404861

^[1]; Tang, Sishuang ^[1]; Li, Zhao ^[1]; Wang, Maoyu ^[2]; ^[3]; ^[4]; Zhan, Xun ^[1]; ^[2]; ^[1]

Univ. of Texas, Austin, TX (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Univ. of Electronic Science and Technology of China, Chengdu (China)
Sichuan Univ., Chengdu (China)

Harvesting recyclable ammonia (NH₃) from the electrocatalytic reduction of nitrate (NO₃RR) offers a sustainable strategy to close the ecological nitrogen cycle from nitration contamination in an energy-efficient and environmentally friendly manner. The emerging intermetallic single-atom alloys (ISAAs) are recognized to achieve the highest site density of single atoms by isolating contiguous metalatoms into single sites stabilized by another metal within the intermetallic structure, which holds promise to couple the catalytic benefits from intermetallic nanocrystals and single-atom catalysts for promoting NO₃RR. Herein, ISAA In-Pd bimetallene, in which the Pd single atoms are isolated by surrounding In atoms, is reported to boost neutral NO₃RR with a NH₃ Faradaic efficiency(FE) of 87.2%, a yield rate of 28.06 mg h^-1 mg_Pd^-1, and an exceptional electrocatalytic stability with increased activity/selectivity over 100 h and 20 cycles. The ISAA structure induces substantially diminished overlap of Pdd-orbitals and narrowed p-d hybridization of In-p and Pd-d states around the Fermi level, resulting in a stronger NO₃^- adsorption and a depressed energy barrier of the potential-determining step for NO₃RR. Finally, further integrating the NO₃RR catalyst into a Zn-NO₃^- flow battery as the cathode delivers a power density of 12.64 mW cm^-2 and a FE of 93.4% for NH₃ production.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Welch Foundation

Grant/Contract Number:: AC02-06CH11357; SC0019019

OSTI ID:: 2404861

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 25 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Intermetallic Single-Atom Alloy In–Pd Bimetallene for Neutral Electrosynthesis of Ammonia from Nitrate

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