INTRODUCTION
• Anthropogenic nitrogen activation starts by converting N 2 and
steam-methane-reformed H2 to NH3 via the Haber–Bosch process
at elevated temperatures and pressures.
• The nitrogen activation/deactivation cycle is energy-intensive as a
result of the reliance on an inert mediator (N ≡ N bond, 941 kJ
mol−1)
• The electrochemical conversion of activated-nitrogen-containing
wastes (nitrate, nitrile, NOx) offers an alternative nitrogen cycle,
one that can potentially be implemented under mild condition
Co-electrolysis of NO3 − and CO2
• Synthesizing urea from NO3− by co-
feeding CO2 is a multistep reaction
involving 16 electrons being transferred
for each urea molecule.
• The first C−N bond formation
(intermediate *CO2NO2) and the
protonation of *CO2NH2 to *COOHNH2
• Single-component metals known to prefer
CO2RR and NO3RR over HER. We found
that Cu, Sn, Bi, Zn and Ag enable modest
levels of urea synthesis
• C-N coupling is favoured by Zn And
Protonation is favoured by Cu.
• The resulting catalyst shows a urea
production rate of 16 µmol h−1 cm−2 (60
mmol h−1 gcat −1) at −0.8 V versus RHE
• GHG emissions are 0.28 kg CO2e kg−1 for
the electrochemical route compared to
1.8 kg CO2e kg−1 for the conventional route
EXPERIMENTAL SETUP
• Single-component Cu catalysts were
prepared by sputtering Cu (200 nm)
on PTFE fibre substrate
• The Zn/Cu hybrid catalysts were
prepared by spray-coating Zn
nanoparticle ink onto a sputtered or
spray-coated Cu film
• Ag/AgCl electrode - reference
electrode
• nickel foam - counter electrode.
• The catholyte but was 0.1 M KHCO3
with 500 ppm KNO3. The anolyte was
always 1 M KOH solution.
• The Zn/Cu hybrid catalysts are
based on metallic phases with
predominant crystalline facets
Steering selectivity to urea on Zn/Cu catalysts
• The ratios between FEC−N-coupling and FEnon-C−N-coupling
indicate selectivity to C−N coupling compared to
non-C−N-coupling reactions
• HER and CO2RR dominate on single-component Zn
and Cu catalysts.
• CO2 is mainly converted to formate on the Zn
catalyst and C2+ products on Cu. By contrast, the
Zn/Cu hybrid catalyst exhibits FECO2RR/FEC−N-
coupling and FEHER/FEC−N-coupling values of 0.13 and
0.16.
• Considerable NO3RR-produced ammonia was
detected only on Cu
• Catalyst, Zn–0.5/Cu, exhibits a potential-
dependent product distribution, with peak FE at
−0.6 V versus RHE.
• The competition of HER dominates when the
potential is below −0.8 V versus RHE.
• HER diminishes as the nitrate concentration
increases, and CO2RR does not change much. The
urea selectivity varies from 50% at 100 ppm NO3 −
[N] to 75% at 1,000 ppm
In-situ Infrared Reflection–Absorption Spectroscopy (IRRAS)
• The infrared bands probed at 1,629 and 1,175 cm−1 originate from
the bending and rocking modes of –NH2 in urea, respectively.
• The band at 1,314 cm−1 is attributed to the wagging mode of –NH 2.
• The infrared band at 1,417 cm−1, related to the stretching mode of
the C–N bond in urea appears when applying negative potentials,
but diminishes when elevating the potential to −1.2 V versus RHE.
• Compared to free urea, the stretching frequency of the C–N bond
shifts to a lower wavenumber, indicating that the urea is
coordinated with metal ions on the hybrid catalyst through an
oxygen atom associated with the C=O group.
• A band at 1,694 cm−1 was observed to appear starting at −0.3 V
versus RHE, diminishing to near zero at −1.2 V versus RHE, the
range over which urea synthesis occurs. This band has assigned to
C=O in the COOHNH2 dimer.
• An infrared band arose at 1,403 cm−1 under potentials between 0
and −1.2 V versus RHE is assigned to the OCO vibrational band,
consistent with the presence of *CO2NH2.
• These results agree with the picture in which protonation of
CO2NH2 to COOHNH2 is a key step for urea synthesis
In-Situ SERS
• Ammonium carbamate (NH2COONH4, AC) - • The *CO2NH2 signal was observed at ~−0.5 V
reference; this consists of CO2NH2 − , NH4 + , versus RHE under urea synthesis conditions
HCO3 − and CO3 2−. and −0.3 V in the AC solution.
• Peak at 334–337 cm−1, the feature assigned • On single-component Cu, we observed the
to M–OCONH2 (*CO2NH2), was detected under *CO2NH2 signal only in the AC solution,
urea synthesis conditions and in the AC starting at −0.1 V versus RHE
solution, but not in KHCO3 solution
DFT studies
• Adsorption and reduction of NO3 −
on the
Zn surface.
• A CO2 molecule inserts to form a C−N
bond, with its oxygen atom bonded to
another Zn atom to form *CO2NO2 (step 2).
• This step is more energetically favourable
on the Zn surface than on the Cu ).
• The reaction energy for step 9 is higher on
the Zn surface (~1.8 eV) than on the Cu
surface (~0.5 eV), corresponding to the
protonation of *CO2NH2 to form *COOHNH2
• The Zn/ Cu hybrid catalyst implements a
relay catalysis mechanism in which both
Zn and Cu sites are catalytically active and
provide distinct functions.
Three-dimensional (3D) hybrid catalysts
• Zn is distributed uniformly on the Cu
• This catalyst leads to an increased
current density at 1,000 ppm NO3 −
compared to the reference case Zn–
0.5/Cu, while retaining the same high
FE to urea.
• The highest partial current density to
urea was obtained at −0.8 V versus
RHE
• Production rate of 16 µmol h−1 cm−2 and
a mass production rate of 60 mmol h−1
gcat −1 at a loading of 0.27 mg cat cm−2
• After operating the catalyst for 32 h at
its optimal potential, that the current
density was constant to within 5%,
and its FE remained within 10%
absolute of its initial value.
• The spent catalyst maintained its
morphology and structure.
Life cycle assessment
• The CED when producing urea
electrochemically is similar to that of
conventional production
• When grid electricity is used, a large portion
of the GHG emissions come from the
electricity consumption for the
electrochemical cell
• When powered by renewable electricity, the
GHG emissions for conventional production
are slightly reduced from 1.2 to 1.1 kg CO 2e
per kg urea
• The ideal scenario for electrochemical
production of urea from nitrogen in
wastewater therefore entails the use of
renewable electricity
Conclusion
• The hybrid catalyst studied here provides an advance in
urea selectivity, achieving 75% FE in simulated wastewater
containing 1,000 ppm NO3 − [N].
• Control experiments, in situ spectroscopy and calculations
paint a picture where the Zn/Cu hybrid catalyst enables
independent tailoring of barrier energies.
• For each of the two steps (the first C−N bond-formation
step and the protonation step from *CO2NH2 to *COOHNH2),
thus providing a relay catalysis path and enabling the
increase in urea selectivity.
• Results add to the urgency of calls to pursue ever-
increasing levels of renewable electricity in the grid.
Hybrid catalysts with high
production rate
• . For the Zn-0.5/Cu sample, Zn and Cu elements are exposed to the
surface with a ratio of about 1.4, and the amount of Zn decreases
gradually while that of Cu increases
