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@INPROCEEDINGS{LunaBarron:1020298,
author = {Luna Barron, Ana Laura and Azua Humara, Ana Daniela and
Eichel, Rüdiger-A. and Mechler, Anna},
title = {{I}nsights into {E}fficient {E}lectrochemical {N}itrate
{R}eduction to {A}mmonia: {R}eaction {E}nvironment and
{M}etal {E}lectrode},
reportid = {FZJ-2024-00043},
year = {2023},
abstract = {The ammonia economy is mainly driven by the inorganic
fertilizer demand. Around $70\%$ of worldwide ammonia
production is used as feedstock for fertilizers. The global
ammonia production is about 176 Mt per year, and it is
expected to increase by $40\%$ by 2050. 1,2 However, the
actual ammonia economy seriously pollutes the air, soil, and
water, contradicting climate neutrality goals. Pollution
comes from different parts of the ammonia value chain, from
its production to its transformation as fertilizers. While
fertilizers are essential in providing sufficient food to
feed our planet, they have been the main cause of water
pollution. Fertilizers are the source of nitrogen nutrients
(nitrates, NO3- ), which allow crops to grow. However, less
than $50\%$ of the applied nitrates nurture crops, while the
rest inevitably leaches to the groundwater, polluting water.
A high level of nitrates makes water unsuitable to drink and
harms the natural environment, particularly via
eutrophication.3 Therefore, it is of vital importance to
develop sustainable technologies that allow treating water
from nitrates. Electrocatalysis is a promising technology
for such a challenge. Electrocatalysis could not only
eliminate nitrates from water, but also conveniently convert
them back into ammonia, generating an added value apart from
nitrogen remediation. Although electrocatalytic nitrogen
reduction to ammonia is promising, its practical application
is hindered by the lack of an electrocatalyst that
simultaneously can show high stability, activity, and
selectivity. For instance, some transition metal-based
electrocatalysts (e.g., Rh, Pt, Cu, Ir) have shown
appreciable activity, but not simultaneously selectivity
towards ammonia in acidic or alkaline media.4,5 Clearly, the
development of a “champion electrocatalyst” for such a
reaction is not trivial. Our primary research focus is to
tailor electrocatalyst properties for nitrates to ammonia
rationally by identifying active sites favorable for
efficient ammonia evolution and understanding the effect of
the reaction environment (nitrate concentration, pH, applied
voltage, and presence of other ions) on activity and
selectivity.As the initial phase of our research, the
electrochemical investigation was carried out using metal
foil electrodes (Ti, Ag, Au, Cu, Bi, Pd, Zn, Ta, and Mo). We
observed that in a reaction environment rich in protons
(i.e., pH 1), selectivity towards ammonia increases with
nitrate concentration. In such an acidic media, the highest
faradaic efficiencies (FE) to NH3 were reached at an applied
potential of -1V versus RHE for most of the tested metal
foils. For example, Ti reached a faradaic efficiency of
$34\%$ with a current partial density to ammonia of -36 mA
cm-2 using 0.4M [NO3-] at pH 1. Because an acid media of pH
1 with a high concentration of nitrated (0.4 M) favored the
formation of ammonia, the intrinsic activity of the metals
was investigated at such conditions at -1V vs. RHE, Figure
shown. Ti, Au, and Cu showed the highest efficiency with
notable corrosion resistance. The effect of higher pH was
also investigated, showing Cu, Au, Ti, and Ag can also
catalyze ammonia formation in specific pH conditions.},
month = {Dec},
date = {2023-12-04},
organization = {GeCatS Infoday "Electrification of
catalytic processes", Frankfurt
(Germany), 4 Dec 2023 - 4 Dec 2023},
subtyp = {Outreach},
cin = {IEK-9},
cid = {I:(DE-Juel1)IEK-9-20110218},
pnm = {1232 - Power-based Fuels and Chemicals (POF4-123) / iNEW2.0
(BMBF-03SF0627A)},
pid = {G:(DE-HGF)POF4-1232 / G:(DE-Juel1)BMBF-03SF0627A},
typ = {PUB:(DE-HGF)24},
doi = {10.34734/FZJ-2024-00043},
url = {https://juser.fz-juelich.de/record/1020298},
}