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Figure 3. Electrochemical performance. a) The LSV curves of the BP/Nb2 C composite in the 0.01 M K2 SO4 with or without 0.05 M KNO3 saturated
electrolyte, and the LSV curves of the BP/Nb2 C composite, BP nanoflakes, and Nb2 C nanosheets measured in 0.1 M K2 SO4 containing NO3 − (inset).
b) NH3 yield rates and c) Faradaic efficiencies of the BP/Nb2 C composite at various applied potentials. d) Comparison of the NH3 Faradaic efficiency of
the BP/Nb2 C composite with other reported electrocatalysts. e) Comparison of the amount of produced NH3 under four different conditions. f) 1 H NMR
spectra of the electrolyte fed by K14 NO3 and K15 NO3 after NO3 − RR by the BP/Nb2 C composite. g) The long-term stability of the BP/Nb2 C composite
with time-dependent current density curve and yield (insets) in a flow electrolyzer at −0.5 V versus RHE for the duration of 10 h. h) LSV cycling tests of
the BP/Nb2 C composite. i) Cycling tests of the BP/Nb2 C composite at −0.5 V versus RHE under ambient conditions.

suggesting that the produced ammonia totally originates from
electrochemical NO3 − RR.[51]
The electrochemical NO3 − RR process for ammonia synthesis
involves the transfer of eight electrons and several possible in-
termediates, including NO2 , NO2 − , NO, N2 O, N2 , NH2 OH, NH3 ,
and NH2 NH2 . In fact, the NO3 − RR process can be considered
as a successive hydrogenation process,[52] and the step for the
hydrogenation of nitrate to produce nitrite is very critical.[53] Ac-
cording to the standard curve at 𝜆 = 540 nm, the NO2 − FE of the
BP/Nb2 C composite is found to be as low as 7.01% at −0.5 V ver-
sus RHE (Figures S10 and S11, Supporting Information), indi-
cating that the NO3 − RR towards the production of NO2 − is in-
hibited. Given that the total FE of NH3 and NO2 − is 97.36%,
which is close to 100%, it can be inferred that there are almost
no other by-products in the NO3 − RR process.[4a,54] Consecutive
electrolysis tests at −0.5 V versus RHE were performed to probe
the durability of the BP/Nb2 C composite. The chronoamperome-
try test for 10 h of continuous NO3 − RR electrolysis presents a very
steady current density (Figure 3g). The accumulated amount of
NH3 for NO3 − RR by the BP/Nb2 C composite at different time
intervals also shows a good linear upward trend (the inset of
Figure 3g), suggesting that the BP/Nb2 C composite has a stable
ammonia yield for nitrate reduction. The neglectable fluctuation
in FEs and NH3 yields during the tests for a total of 15 cycles fur-
ther confirms the excellent stability of the BP/Nb2 C composite for
NO3 − RR (Figure 3i).[55] Besides, no obvious change is observed
on the LSV curves of the BP/Nb2 C composite after 500 cycles,
also corroborating the high stability of the BP/Nb2 C composite
for NO3 − RR (Figure 3h). The characterizations of the BP/Nb2 C
composite before and after cycling tests by SEM and TEM re-
vealed that the microscopic morphology of the BP/Nb2 C compos-
ite still maintains a layered structure without obvious changes af-
ter cycling experiments (Figures S12 and S13, Supporting Infor-
mation), indicating the good durability of BP/Nb2 C composite.
Moreover, the Nb 3d, P 2p, and O 1s XPS spectra of the BP/Nb2 C
composite after cycling experiments are almost the same as the

Adv. Energy Mater. 2023, 13, 2301136 2301136 (6 of 13) © 2023 The Authors. Advanced Energy Materials published by Wiley-VCH GmbH