S c i e n c e A d v a n c e s | R e s e ar c h A r t i c l e

CHEMISTRY Copyright © 2024 The

Authors, some rights
Onsite ammonia synthesis from water vapor and reserved; exclusive
licensee American
nitrogen in the air Association for the
Advancement of
Science. No claim to
Xiaowei Song1†, Chanbasha Basheer2*†, Jinheng Xu1, Richard N. Zare1* original U.S.
Government Works.
An innovative method for onsite ammonia synthesis under ambient conditions has been developed using a cata- Distributed under a
lyst mesh composed of magnetite (Fe₃O₄) and Nafion polymer. We pass air through the catalyst, which condenses Creative Commons
microdroplets from atmospheric water vapor and uses nitrogen from the air, resulting in ammonia concentrations Attribution
ranging from 25 to 120 μM in 1 hour, depending on local relative humidity. Operated at room temperature and NonCommercial
atmospheric pressure, this technique eliminates the need for additional electricity or radiation, thereby substan- License 4.0 (CC BY-­NC).
tially reducing carbon dioxide emissions compared to the traditional Haber-­Bosch process. In laboratory experi-
ments, we further optimized the reaction conditions and scaled up the process. After 2 hours of spraying, the

Downloaded from [Link] at Indian Institute of Technology, Madras on April 23, 2025
ammonia concentration increased to 270.2 ± 25.1 μM. In addition, we present a portable device designed for
onsite ammonia production which consistently produces an ammonia concentration that is adequate for some
agricultural irrigation purposes.

INTRODUCTION Nitrogen is readily extracted from the air by aerosols, mist, and
Ammonia (NH3) is the second most produced chemical globally, cloud droplets through wet and dry deposition processes. Nitrogen-­
with an annual production of 183 million metric tons (1). It is pri- containing compounds, such as ammonia (NH₃) and nitrogen oxides
marily used for energy transport, fertilizer production, and the syn- (NOx), can dissolve in or adhere to cloud droplets, facilitating their
thesis of fine chemicals (2, 3). The Haber-­B osch process is the removal from the air (23). Liu et al. (24) demonstrated that nitrogen-­
predominant method for ammonia synthesis, using methane (CH4) containing cloud droplets can chemically change to accelerate their
as a hydrogen source and an iron-­based catalyst to break the N≡N accumulation. Recently, we developed a method for onsite ammonia
triple bond and reduce it under high temperatures (350° to 450°C) and hydrazine production by spraying water microdroplets mixed
and high pressures (150 to 200 bar) (4, 5). This process accounts for with nitrogen gas through a Fe3O4-­Nafion–coated CuO mesh (25).
over 2% of global energy consumption and 5% of natural gas usage, This gas-­liquid-­solid heterogeneous catalytic system produced ap-
contributing substantially to greenhouse gas emissions (6, 7). Con- proximately 61.9 ± 2.2 μM of ammonia, demonstrating the effective-
sequently, there is an urgent need for developing environmentally ness of our approach. Density functional theory simulations were
friendly and sustainable ammonia synthesis methods. used to explore the catalytic mechanism, revealing that water micro-
Recent research has focused on electrochemical catalysis as a droplets act as both a reducing agent and a reaction medium in the
cost-­effective alternative to the energy-­intensive Haber-­Bosch pro- presence of the catalyst.
cess (8–11). By applying controlled electrochemical potentials, N₂ In this study, we build on this previous work and aim to further
can be hydrogenated at lower temperatures and pressures, thereby develop an onsite ammonia synthesis method using nitrogen and
reducing energy requirements. Electrochemical ammonia synthesis water vapor in the air. We investigated the effects of environmental
often involves rare metals such as Ru, Pt, Pd, Mo, Nb, and Au (12–18). conditions, such as relative humidity, wind speed measured at the
For instance, Fu et al. (18) developed a continuous flow reactor catalyst mesh, salinity, and pH, on ammonia production. In addi-
using a PtAu alloy for hydrogen oxidation coupled with lithium-­ tion, we examined the influence of water microdroplet size, electro-
mediated nitrogen reduction, achieving a Faraday efficiency of 61 ± lyte concentration, contact electrification potential, and current on
1% and an energy efficiency of 13 ± 1% at room temperature. ammonia synthesis. The optimal formulation of two critical catalyst
Water offers a cleaner and more widely available alternative to components, Fe3O4 and Nafion, was systematically explored to de-
methane and hydrogen gas as a hydrogen carrier. Recent studies have termine the favorable reduction potentials for ammonia production
highlighted the unique physicochemical properties of micrometer-­ and to better understand the role of water microdroplets and cata-
sized water droplets, including single-­electron transfer between interfa- lytic composition. Last, we constructed a prototype device and dem-
cial H+ and OH− to form H· and OH· radicals and spontaneous redox onstrated that it is capable of scaling ammonia production to the
processes (19, 20). In addition, contact electrification across the tri-­ millimolar level in laboratory conditions.
interface (water microdroplet, air, and solid catalyst) can drive electro-
synthetic processes (21, 22). This phenomenon presents an opportunity
to leverage water and atmospheric nitrogen for ammonia production. RESULTS
Design and operation of an onsite ammonia
production device
1
Department of Chemistry, Stanford University, Stanford, CA 94305, USA. 2Chemis- An onsite ammonia production device, illustrated in Fig. 1, has been
try Department, King Fahd University of Petroleum and Minerals, Dhahran 31261, engineered for the efficient and sustainable synthesis of ammonia
Saudi Arabia.
*Corresponding author. Email: cbasheer@​kfupm.​edu.​sa (C.B.); zare@​stanford.​edu
using nitrogen and water vapor in the air as primary reactants. This
(R.N.Z.) device uses a catalytic mesh that enhances the conversion of nitro-
†These authors contributed equally to this work. gen and water microdroplets (present as water vapor or mist) into

Song et al., Sci. Adv. 10, eads4443 (2024) 13 December 2024 1 of 9

S c i e n c e A d v a n c e s | R e s e ar c h A r t i c l e

(Fig. 2, A and B). In contrast, the offline collected sample from

spraying water microdroplets through the Fe3O4-­Nafion@CuO
mesh exhibited a significant enhancement in the intensity at m/z 36
([NH4OH + H]+), with an increase by a factor of 3000, which is
sixfold higher than previously observed in the online-­MS monitoring
experiment (Fig. 2C). Conversely, the intensity at m/z 55 (N2H4 + Na)+
was only 30% of that detected in the online experiment.
These findings suggest that the offline spraying and recycling sys-
tem produces more ammonia and less hydrazine, the latter being a
nitrogen reduction intermediate. Furthermore, to differentiate the
[NH4OH + H]+ species from [H3O + OH•]+, hydrogen-­deuterium
exchange (HDX) MS was used. This method distinguished success-
fully between the two species based on their exchangeable proton
numbers and isotope distribution patterns (fig. S1).

Downloaded from [Link] at Indian Institute of Technology, Madras on April 23, 2025
We conducted a supplementary experiment focusing on nitrous
oxygenate species. We found that the NO2− ion at m/z 46 decreased
and the NO3− at m/z 62 increased when spraying water microdrop-
lets into the catalyst region. In contrast, when spraying onto the Cu
and CuO region, both NO2− and NO3− were increased (fig. S2). Re-
cent reports have demonstrated that the nitrous oxygenate species
can be generated across the air-­water interface of microdroplets be-
cause of the presence of interfacial reactive oxygen species (26). This
nitrogen oxidation process might be further enhanced when em-
ploying the Fenton’s reagents such as Fe(II) or Cu(II) (27, 28). These
facts point out the direction for our next step improvement in the

Fig. 1. Diagram of the onsite preparation of green ammonia. (A) Schematic of

the onsite ammonia production device consisting of a catalyst mesh, cooling con-
denser plate for capturing the harvested water sample, and collector. Natural wind
and a fan embedded in the device can provide passive and active driving forces
respectively for causing water vapor and nitrogen in the air to pass through the
catalyst mesh. (B) Photograph of the device in operation on the Stanford campus.

ammonia. The operational mechanism involves a suction pump that

draws in ambient air, ensuring consistent exposure of nitrogen and
water vapor or water microdroplets to the catalytic surface. This in-
teraction promotes contact electrification, which is crucial for driv-
ing the ammonia synthesis process. The resultant ammonia-­enriched
aqueous solution is subsequently collected by a condenser plate,
effectively separating it from the air and water vapor in the chamber.
The device’s design allows for decentralized ammonia production,
reducing transportation and storage needs while using nitrogen and
water vapor in the air as abundant reactants.

Verification of ammonia production via MS detection

In our previous work, we demonstrated the generation of ammonia
using online spraying coupled with mass spectrometry (MS) moni-
toring. To eliminate artefactual signals, the sample solution contain-
ing reaction products was collected offline and analyzed by MS. In the
control experiments, where direct air/water spraying was conducted
either without a catalyst or through a CuO foam, the mass spectro-
metric analysis revealed only the presence of hydrated sodium [mass/ Fig. 2. Identification of products generated from the continuous spraying-­
charge ratio (m/z) 41, [H2O + Na]+; and m/z 59, [2H2O + Na]+], recycling setup for ammonia synthesis. Mass spectra of solutions collected from
hydrated potassium (m/z 57, [H2O + K]+), and hydroxyl radicals continuously spraying water and air through (A) no catalyst foam, (B) a copper
combined with hydronium cations (m/z 36, [H 3 O + OH•] + ) oxide foam, and (C) copper oxide foam coated with Fe3O4/Nafion.

Song et al., Sci. Adv. 10, eads4443 (2024) 13 December 2024 2 of 9

S c i e n c e A d v a n c e s | R e s e ar c h A r t i c l e

catalyst formula. We should either replace the CuO mesh with a dif- Catalyst optimization and contact electrification
ferent one to avoid oxidation by-­products or intentionally use CuO current measurement
to oxidize the nitrogen into nitrate followed by further reduction Because no external electrical potential is applied to the system, this
into ammonia, which is relatively easier than direct reduction from fact motivates us to explore the source of energy that drives this ni-
nitrogen (29). trogen reduction reaction. We used a picoammeter to precisely re-
cord the current generated by spraying air/water onto a catalyst
Isotope-­labeled nitrogen for online MS testing mesh (fig. S5). The electronic probe was connected to the catalyst
To ensure that the ammonia produced is free from contamination, mesh for the current measurement (Fig. 4A). Figure 4B shows the
we introduced isotope-­labeled nitrogen (15N2) to replace the com- current generated from varied amounts of Fe3O4 and Nafion. Re-
pressed nitrogen as the nebulizing gas (Fig. 3A). Acetone (1%) was sults indicate that a higher Nafion percentage resulted in a negative
added to the water to capture the generated ammonia and facilitate current, whereas a higher amount of Fe3O4 resulted in a positive
its detection within the MS range (setup shown in fig. S3). The gen- current. An optimal balance between these components is necessary
erated ammonia condenses with acetone to form an imine structure for achieving maximum ammonia production. Figure 4C shows the
having a molecular weight exceeding 50, suitable for high-­resolution correlation between ammonia production and different composi-
m/z data recording (Fig. 3B). As shown in Fig. 3C, the produced

Downloaded from [Link] at Indian Institute of Technology, Madras on April 23, 2025
tions of Fe3O4 and Nafion. We found that the catalyst with a ratio of
ammonia was identified almost exclusively as 15NH3, which con- 0.7 wt % Nafion to 6 mg of Fe3O4 gave the highest ammonia produc-
firms that the source of nitrogen atoms in ammonia originates from tion estimated by the MS quantitation curve (fig. S6). This composi-
the N2 surrounding the water droplets. tion corresponds to a current density around −1.0 μA/cm2, which
differs from the highest current density of −1.8 μA/cm2. This result
Spectroscopic ammonia detection revealed that a moderate current (potential) was the optimal driving
Ammonia was also identified by ultraviolet-­visible (UV-­Vis) and force. We also validated this result by investigating different external
Raman spectroscopy. Sample solutions prepared with and without potentials on the catalyst mesh to confirm that a negative potential
catalyst were also tested using the indophenol blue colorimetric of −0.1 V was sufficient to achieve optimal ammonia yield (fig. S7).
method (30). The solution’s color turned yellow for the sample col- The measurement of the current generation from spraying air-­
lected from direct spraying without catalyst. In contrast, the sample water microdroplets through the catalyst mesh clearly indicates the
collected from spraying air/water through the catalyst gradually existence of contact electrification between water-­solid, water-­gas,
changed its color from light to dark green. UV-­Vis spectroscopy and solid-­gas phases. The interfacial charge/electron separation and
confirmed the sample’s maximum absorbance to be at the wave- transfer indeed happens during this process (31, 32). Extremely
length of 690 nm. The UV-­Vis profile of the sample solution is con- close contact between any of the two phases above is also expected
sistent with the profile from the ammonia standard (Fig. 3D). The to generate a strong static electric field as the driving force in nu-
Raman spectroscopy also confirmed that the sample’s peaks at 1090 merous water microdroplet “mini-­electrochemical cells.” Our previ-
and 550 cm−1 match the ammonia standard (fig. S4). ous calculation supports that N2 will be absorbed to the Fe3O4

Fig. 3. Ammonia verification by high-­resolution MS and UV-­Vis spectroscopy. (A) Diagram of the on-­line MS monitoring of the ammonia generated by spraying
isotope-­labeled/native nitrogen gas– and acetone-­contained water through the catalyst mesh. (B) Diagram of the nitrogen reduction to ammonia, capture process, and
target products. (C) Mass spectrum revealing the formation of isotope-­labeled ammonia. (D) UV-­Vis spectra obtained from one sample, one negative control, and two
ammonia standard solutions by the colorimetric test.

Song et al., Sci. Adv. 10, eads4443 (2024) 13 December 2024 3 of 9

S c i e n c e A d v a n c e s | R e s e ar c h A r t i c l e

Downloaded from [Link] at Indian Institute of Technology, Madras on April 23, 2025
Fig. 4. Catalyst formula investigation and contact electrification current measurement. (A) Setup for the measurement of current generated from the air-­water
microdroplets passing through the catalyst mesh. The inset is the diagram presenting the role of water microdroplets, iron oxide, and Nafion in the nitrogen reduction, as
well as the contact electrified water and catalyst interfaces to form the electric field as the driving force for the nitrogen reduction. (B and C) Plot of current density change
with varied amount of iron oxide and Nafion percentage.

surface followed by stepwise addition of hydrogen atoms donated density changes by regulating the amount and size of water micro-
from water microdroplets (H atom or H+/e−). In this process, the droplets and their relative speed passing through the catalyst mesh.
perfluoroalkyl backbone of Nafion polymer can facilitate the elec- Figure 5A shows that the current on the mesh changed from 1.2 to
tron (e−) transfer because of its strong electronegativity to stabilize 14.4 μA/cm2 with an increase of relative humidity from 30 to 90%.
e−. In addition, sulfite groups (SO3H) on the Nafion polymer can Although a relative humidity of over 50% raises the current density
also facilitate the H+ transfer to the nitrogen atom. An electric field by introducing more water droplets, it did not substantially in-
will be formed across the negatively charged catalyst mesh and pos- crease the droplet size distribution (fig. S9). Meanwhile, it can
itively charged water microdroplet surfaces. This explains the ob- also make the catalyst site fully hydrated from contacting nitrogen
served negative current and slight negative potential, which drives gas molecules.
the nitrogen reduction. We have conducted the measurement of microdroplet size distri-
bution under different water flow velocities. We found the influence
Influence of microdroplet and catalyst mesh pore size of water flow speed is complex. A bimodal distribution pattern will
The combination of microdroplet size distribution and catalyst be formed given a too low (15 μl) or a too high speed (100 μl/min).
mesh size determines the ammonia production. Given the stable A uniform distribution was form when the speed is moderate at
distribution of microdroplets (30 to 50 μm) generated by a nozzle 50 μl/min. Although the numbers of large droplets are minor, they
sprayer, we compared the ammonia level generated by catalyst do influence the weighted-­average diameter. Statistically speaking,
meshes with different pore sizes (50, 100, 200, and 400 μm). It is average droplet size shrinks from 50 to 30 μm with the flow rate
found that the mesh with average pore size of 100 μm can achieve changed from 10 to 100 μl/min. The average size becomes stable
the highest amount of ammonia when the average microdroplet size when the flow rate is higher than 50 μl/min (fig. S10). Compared to
at 30 μm. Given an average microdroplet size of 50 μm, the mesh the influence of relative humidity, the wind speed influence was
with an average size of 150 μm can achieve optimal concentration minor. The wind speed mainly influences the linear speed of drop-
(fig. S8). Mesh with too large a pore size cannot make gas and water lets and the amount of microdroplets per second passing through
droplets effectively interacted with catalyst to generate the contact the catalyst mesh. There was no significant difference in average
electrification. Mesh with too small a pore size cannot let the gas and droplet sizes with the wind speed ranging from 5 to 13 miles per hour
water microdroplets pass through but makes them condense. (mph; fig. S11).
Figure 5B shows that the amount of salt in water microdroplets
Influence of environment on electrification and raises the current density on the catalyst’s surface. This may be at-
ammonia generation tributed to the fact that salt in water serves as an electrolyte and in-
For the onsite ammonia production, many factors in the natural creases the conductivity of the catalyst mesh. In addition, the effect
environment, such as wind speed, humidity, saltiness, and pH, can of water pH on ammonia production was investigated (Fig. 5C).
influence the contact electrification current that provides the native Slightly acidic conditions (pH 5 to 6) were more favorable. Conse-
driving force for ammonia electrosynthesis. Wind speed and rela- quently, in onsite applications of this method, the pH value was
tive humidity are two conjugative factors that may cause current maintained between 5.0 and 6.0.

Song et al., Sci. Adv. 10, eads4443 (2024) 13 December 2024 4 of 9

S c i e n c e A d v a n c e s | R e s e ar c h A r t i c l e

Downloaded from [Link] at Indian Institute of Technology, Madras on April 23, 2025
Fig. 5. Influence of environmental conditions the generated current and onsite ammonia preparation. (A) Heatmap of current density generated with varied relative
humidity and wind speed. (B) Influence of salt concentration on the current density on the catalyst mesh. (C) Influence of water pH on the ammonia production.
(D) Concentration of ammonia produced from different locations.

Onsite ammonia preparation still has a negative impact on ammonia generation by shielding the
On the basis of these findings, we selected 9 locations in the Bay Area water-­air interface contacting the catalyst mesh. Because conductiv-
(fig. S12) with different relative humidity, temperature, and wind ity is not the only factor that can guarantee the reaction. As we
speed values for the field tests (table S1). At the start of the field ex- have stated before, the ammonia generation can reach the highest
periment, a precooled glass slide was used to harvest the condensed concentration when the generated contact potential was around
water vapor as the control, which showed a baseline ammonia level of −100 mV. Given the constant resistance of catalyst mesh, a further
16.9 ± 2.3 μM. After subtracting the baseline value from each place, higher current means a higher voltage which does not favor the
Fig. 5D shows the range of ammonia concentrations that were made reaction either.
onsite, which ranged from 25 to 120 μM. Checking weather informa- The influence of pH on ammonia synthesis is consistent both in
tion, we learned that a higher temperature and a lower relative hu- the dehumidifier-­based onsite method and the nozzle spray-­based
midity create a relatively dry environment that can easily cause scale-­up method. The interfacial charge transfer, considered critical
contact electrification and make smaller sized droplets. Therefore, the to the nitrogen reduction process, will decrease monotonically, in
ammonia production increased from 25 to 60 μM to a substantially particular under strong acidic conditions. This effect receives ex-
higher level. High humidity and low temperature, especially near the perimental and theoretical support from recent reports on water
sea or lake side, makes water vapor easily condense to form larger vapor contacting silica particles to generate hydroxyl peroxide, urea
droplets, which is unfavorable for ammonia production. synthesis from water, carbon dioxide, and nitrogen, and ammonia
synthesis from water and nitrogen via contact electrification (32–34).
Scaling-­up ammonia production Nonetheless, this developed spraying-­recycling system has shown
A spraying-­recirculating system was developed for continuous its potential in the green synthesis of ammonia with ordinary water,
ammonia production (Fig. 6A). Different water sources were inves- provided desalination can be introduced (35).
tigated including ocean water, tap water, and deionized water. It After 2 hours of running, the rate of the ammonia generation
was found that the deionized water can yield the highest concentra- slowed down with a plateau level of approximately 260 μM (Fig.
tion (140 μM), whereas the tap water achieved a concentration of 6C). This is attributed to the accumulation of produced ammonia in
100 μM. Subtracting the baseline level of ammonia that existed in the the recycled water. To make further concentration improvement,
ocean water sample, there was still approximately 45 μM ammonia we introduced a zeolite absorbent into the bottom of the reaction
produced from the spraying-­recycling process using ocean water chamber to enrich ammonia from the spraying-­recycling system.
within 1 hour (Fig. 6B). Fifty micromolar ammonia was produced without zeolite precon-
Although micromolar level of salt concentration helps to in- centration, whereas the zeolite-­containing recycling system ab-
crease the conductivity of microdroplets, which is necessary for con- sorbed more than 80% of ammonia. After eluting with 1 mM HCl,
tact electrification as the driving force, too high a salt concentration we obtained an ammonia concentration of 1.4 mM (Fig. 6D).

Song et al., Sci. Adv. 10, eads4443 (2024) 13 December 2024 5 of 9

S c i e n c e A d v a n c e s | R e s e ar c h A r t i c l e

Downloaded from [Link] at Indian Institute of Technology, Madras on April 23, 2025
Fig. 6. Investigating the ammonia scale-­up procedure conditions. (A) Experimental setup. (B) The concentration of ammonia produced with different water sources.
(C) The maximum reaction time in which the ammonia reached a stable level in the spraying-­recycling system. (D) Effect of zeolite absorption and desorption for the 1-­liter
ammonia solution with a concentration of 50 μM.

DISCUSSION In general, it has advantages in decarbonization and decentraliza-

Ammonia is essential for fixing nitrogen in the soil and providing tion, which are both environment-­and customer-­friendly.
the nutrients plants need to grow and thrive (36). Plants can absorb Our research has made substantial strides in nitrogen fixation by
and use different forms of nitrogen from the soil, with ammonium achieving a lower limit of ammonia production. We synthesized the
(NH4+) and nitrate (NO3−) being the most essential inorganic ions. highest ammonia concentration onsite, 120 μM, which is sufficient
NH4+ requires less energy to absorb than nitrate, and most plants fertilizer for some plants/seedlings (38–42). If a zeolite filter is used,
cannot use NO3− directly without first turning it into ammonia (34). the concentration can be raised to the millimolar level. The ammo-
However, only a limited number of plant species thrive when NH4+ nia will be produced and immediately used by integrating the on-­
is the sole or primary nitrogen source. demand preparation process into the irrigation. It not only saves the
Most plants develop toxicity symptoms at high concentrations of effort of shipping fertilizer from factory to market to field and add-
NH4+; for example, more than 0.1 mM concentrations in barley seed- ing it into the irrigation water but also causes no extra fees for ad-
lings lead to leaf chlorosis and severe growth suppression (37). Simi- ditional water and electric use.
larly, aquaponics plants and some selected plants can benefit from Our portable onsite device is a pivotal step toward creating an
NH4+ concentrations as low as 17 to 85 μM; above this range, NH4+ efficient system suitable for further development to improve the scal-
concentrations can be toxic. The specific tolerance varies among ing up to meet the needs of agricultural and industrial use. The pres-
plant species. High ammonia levels (beyond 170 μM) can lead to tox- ent system is truly primitive and needs improvement. In the field, we
icity symptoms in sensitive plants (38–41). Therefore, a tailored am- collected 20 ml/hour and in the lab 500 ml/hour. We believe that
monia and nitrate fertilizer approach is necessary for optimal plant these amounts can be majorly increased with suitable engineering. A
growth and yield. localized, sustainable green ammonia production approach, when
The HB process consumes intensive energy, needs heavy use of developed, would reduce the reliance on large-­scale industrial facili-
fossil fuels, and causes massive carbon dioxide emissions. In con- ties and the associated transportation costs and emissions, contrib-
trast, the feeding nitrogen of our method comes from the air, which uting to a more sustainable agricultural ecosystem.
is free. Hydrogen comes from water, which is clean. The energy
comes from the contact electrification between water and catalyst,
which is green. For the onsite device, the external energy input comes MATERIALS AND METHODS
from the wind energy and the dehumidifier to collect the water va- Reagents and materials
por. For the scale-­up device, the external energy comes from the elec- The ammonium hydroxide solution was purchased from Fisher
tric diaphragm pump to recycle water and spray it into microdroplets. Chemical [30% (w/v), ACS grade]. High-­p erformance liquid

Song et al., Sci. Adv. 10, eads4443 (2024) 13 December 2024 6 of 9

S c i e n c e A d v a n c e s | R e s e ar c h A r t i c l e

chromatography (HPLC)–grade water (Merck, Rahway, NJ, USA) for the identity of ions at m/z 36 and m/z 55. The ammonia ion
was used as solvent for generating microdroplets and diluting the ([NH4OH + H]+) should have 6 exchangeable protons and the hy-
ammonia solution. The commercially available colorimetric test kit drazine ion [N2H4 + Na]+ should have 4 protons for HDX.
in the marker was used to detect the ammonia concentration
(item model number: LR8600, Mars Fishcare North America Inc., Onsite ammonia production setup
Chalfont, PA, USA). The compressed air (Prospec UN1002, Ultra The onsite ammonia production device is mainly consisted of sev-
Zero Grade) and nitrogen (UN1066, Grade 5.0, Medipure, by Linde) eral critical functional blocks: (i) air filter embedded with a catalyst
were ordered from Praxair Inc. (Danbury, CT, USA). The isotope-­ mesh that enhances the conversion of nitrogen and water microdro-
labeled nitrogen gas (98 atom% 15N2, 364584-­5L, 12 ATM) and plets (present as water vapor or mist) into ammonia; (ii) a suction
deuterium oxide (D2O, 99.95% for nuclear magnetic resonance pump that draws in ambient air, ensuring consistent exposure of
spectroscopy) was purchased from Sigma-­Aldrich. Zeolite (type nitrogen and water vapor or water microdroplets to the catalytic
ZSM-­5) was acquired from ACROS. Ferrosoferric oxide (black powder, surface; (iii) a cooling system to condense the water vapor into the
Fe3O4) was from Spectrum Chemical MFG Corp. (769 Jersey Ave, liquid form for collection; (iv) the zeolite absorbent packed within
New Brunswick, NJ, USA) and Nafion solution (5 wt %) was acquired the collection funnel to absorb the ammonia for the concentrating

Downloaded from [Link] at Indian Institute of Technology, Madras on April 23, 2025
from the Fuel Cell Earth (10 Draper St, Unit 32, Woburn, MA, purpose; (v) a portable power that can support the normal running
USA). Copper mesh supporter was order from TMAXCN (Xiamen, of the whole system for the on-­field ammonia preparation.
China) and cut into replicates of small pieces for use (loading area,
1.0 × 1.0 cm2; and thickness, 1.6 mm). Continuous-­spraying-­recycling system for scaling-­up
ammonia production
Catalyst preparation The spraying-­recycling setup for scaling the production of ammonia
Different amount of ferrosoferric oxide (F) and Nafion solution (N) consisted of an ultrasonic air atomizing nozzle (cone angle 60°, ADG
were investigated to get the optimal formula. The spiked Fe3O4 SV980, China), a cylinder chamber (ID, 100 mm; and height, 200 mm),
amount was as follows: 0 mg (F1), 1 mg (F2), 2 mg (F3), 4 mg (F4), a catalyst container (ID, 25.5 mm; and height, 20 mm), a peristaltic
6 mg (F5), and 8 mg (F6). The spiked Nafion amount was selected pump (flow rate, 0 to 100 ml/min; and tube ID, 2 mm; Gikfun,
between 0% × 40 μl (N1), 0.1% × 40 μl (N2), 0.5% × 40 μl (N3), 1% China), a gas cylinder (Praxair, San Jose, CA, USA), and Teflon tubing
× 40 μl (N4), 2% × 40 μl (N5), 5% × 40 μl (N6), 5% × 60 μl (N7), 5% (ID, 2 mm; and length, 300 mm). The pneumatic nozzle sprayer
× 80 μl (N8), 5% × 120 μl (N9), and 5% × 160 μl (N10). Therefore, atomizes bulk water into fine water microdroplets. The cylinder
there were 6 levels of Fe3O4 amounts and 10 levels of Nafion amounts chamber is made of glass and used as the reaction container. The
to get 60 different formulas. For each formula, a total amount of 1-­ml catalyst mesh is mounted 90 mm from the cylinder chamber bottom.
catalyst dispersion ink [water-­ethanol, 6:4, (v/v)] was prepared by A peristaltic pump is used to transfer condensed water droplets at
ultrasonication for 2 hours. Then, the 100-­μl dispersion was drop-­ the bottom of chamber back to the nozzle for water microdroplet
casted onto a copper oxide mesh supporter (loading area, 1.0 × 1.0 cm2; regeneration. The water flow rate was kept consistent at 20 ml/min.
and thickness, 1.6 mm; TMAXCN, Xiamen, China) mounted on a Gas cylinder provides the compressed air (Linde, UK) as both the
heating plate at 145°C for fully dried. Thereafter, the prepared cata- nebulizing gas and the nitrogen feeding source, with the pressure
lyst mesh was put into the autoclave for baking under 200°C. set at 100 psi. The deionized, ultrapure water (18.2 megohm-­cm,
Millipore), tap water (2 ohm-­m), and seawater (0.2 ohm-­m) collected
Nozzle spray setup for the ammonia detection by MS at the ocean near the bay area were used as spraying solutions.
A nozzle spray setup consisted of a syringe pump (Masterflex, Cole
Parmer, Vernon Hills, IL, USA), gas cylinder, stainless steel tubing Product identification
[inner diameter (ID), 500 μm; outer diameter (OD), 2 mm; and The existence of ammonia was further confirmed with the indophe-
length, 30 mm], stainless-­steel tee union (Swagelok, Solon, OH, nol blue colorimetric method. The commercially available test kit
USA), and silica capillary (ID, 150 μm; and OD, 250 μm; Polymicro was used to conduct this colorimetric test (item model number:
Technologies, Phoenix, AZ, USA). A linear ion trap mass spectrom- LR8600, Mars Fishcare, USA). For each 1-­ml sample solution, two
eter (LTQ-­MS; Thermo Fisher Scientific, San Jose, CA, USA) was drops of the test kit solution A and two drops of the test kit solution
used for the online ammonia formation monitoring and target B were sequentially spiked and fully shake to observe the color
product identification. The nozzle spray setup was fixed in front of change after 5 min reaction at the room temperature. UV-­Vis spec-
the LTQ-­MS inlet with a 15 mm distance. A solid catalyst mesh troscopy equipped with the 96-­well plate array readout system was
was positioned in the middle of the nozzle sprayer outlet and the used to acquire the sample absorbance within the range of 220 to
LTQ-­MS inlet. The compression air or nitrogen was used as the neb- 800 nm and confirm the maximum absorbance wavelength.
ulization gas with the pressure tuned to 100 psi. The flow rate was
set at 5 μl/min. The LTQ-­MS capillary voltage was set at −40 V, Colorimetric quantitation of ammonia
whereas the lens voltage was at −20 V. The scan range was set at the Two drops of ammonia colorimetric test kit solution A and solution
“low” mode with the m/z 30 to 60. The maximum acquisition time B were added to a 0.5-­ml samples for developing the indication col-
was 400 ms. The capillary temperature was set within range of or after 10 min. For the onsite prepared ammonia, its concentration
300°C. The generation of ammonia was characterized by m/z 36 can be directly readout from the colorimetric chart board within the
([NH4OH + H]+) and by-­product hydrazine was characterized by commercial product. For accurate quantitation in laboratory, a
m/z 55 ([N2H4 + Na]+). The catalytic selectivity for the ammonia quantitation curve will be constructed by a dilution series of am-
versus hydrazine was evaluated by their intensity ratio. The HDX monium hydroxide standard solutions. Specifically, it was first pre-
experiment was conducted to exclude false-­positive interference pared at a concentration of 200 mg/liter [parts per million (ppm)] as

Song et al., Sci. Adv. 10, eads4443 (2024) 13 December 2024 7 of 9

S c i e n c e A d v a n c e s | R e s e ar c h A r t i c l e

a stock solution by diluting with HPLC-­grade pure water. Then, a 5. V. Kyriakou, I. Garagounis, A. Vourros, E. Vasileiou, M. Stoukides, An electrochemical
Haber-­Bosch process. Joule 4, 142–158 (2020).
series of ammonia solutions (0.2, 0.5, 1.0, 2, 5, 10, and 20 ppm) were
6. A. Valera-­Medina, H. Xiao, M. Owen-­Jones, W. I. F. David, P. J. Bowen, Ammonia for power.
prepared by gradual dilution. Three replicates of sample or ammo- Prog. Energ. Combust. Sci. 69, 63–102 (2018).
nia solution at each concentration (0.5 ml each) were measured by 7. A. M. Elbaz, S. Wang, T. F. Guiberti, W. L. Roberts, Review on the recent advances on
the UV-­Vis system using the colorimetric method described above. ammonia combustion from the fundamentals to the applications. Fuel Commun. 10,
After 15-­min colorimetric reaction, the absorbance of solution at 100053 (2022).
8. X. Cui, C. Tang, Q. Zhang, A review of electrocatalytic reduction of dinitrogen to ammonia
the wavelength of 690 nm was used to determine concentration. The under ambient conditions. Adv. Energy. Mater. 8, 1800369 (2018).
calibration curve was plotted by fitting the absorbance corrected by 9. B. H. R. Suryanto, H.-­L. Du, D. Wang, J. Chen, A. N. Simonov, D. R. MacFarlane, Challenges
background subtraction versus the concentration. and prospects in the catalysis of electroreduction of nitrogen to ammonia. Nat. Catal. 2,
290–296 (2019).
10. G. Soloveichik, Electrochemical synthesis of ammonia as a potential alternative to the
Relative humidity and wind speed simulation by
Haber–Bosch process. Nat. Catal. 2, 377–380 (2019).
nozzle spray 11. D. Ye, S. C. E. Tsang, Prospects and challenges of green ammonia synthesis. Nat. Synth. 2,
The basic setup for spraying water microdroplet was as described 612–623 (2023).
above in the “Nozzle spray setup for the ammonia detection by MS” 12. X. Li, T. Li, Y. Ma, Q. Wei, W. Qiu, H. Guo, X. Shi, P. Zhang, A. M. Asiri, L. Chen, B. Tang, X. Sun,
Boosted electrocatalytic N2 reduction to NH3 by defect-­rich MoS2 nanoflower. Adv. Energy

Downloaded from [Link] at Indian Institute of Technology, Madras on April 23, 2025
section. The compressed air (100 psi) is transmitted through a
Mater. 8, 1801357 (2018).
stainless-­steel tubing connected to one entry port of the stainless-­ 13. J. Han, Z. Liu, Y. Ma, G. Cui, F. Xie, F. Wang, Y. Wu, S. Gao, Y. Xu, X. Sun, Ambient N2 fixation
steel tee union (Swagelok, Solon, OH, USA). The other entry port of to NH3 at ambient conditions: Using Nb2O5 nanofiber as a high-­performance
the tee union is connected to a silica capillary (ID, 100 μm; and OD, electrocatalyst. Nano Energy 52, 264–270 (2018).
150 μm; Polymicro Technologies, Phoenix, AZ, USA) for the water 14. J. Zheng, Y. Lyu, M. Qiao, R. Wang, Y. Zhou, H. Li, C. Chen, Y. Li, H. Zhou, S. P. Jiang, S. Wang,
Photoelectrochemical synthesis of ammonia on the aerophilic-­hydrophilic
flow, which is pressured by a syringe pump (Masterflex, Cole Parmer,
heterostructure with 37.8% efficiency. Chem. 5, 617–633 (2019).
Vernon Hills, IL, USA). The gas and water flow through a set of 15. S. Back, Y. Jung, On the mechanism of electrochemical ammonia synthesis on the Ru
co-­axial capillaries to form a fine spray by precisely controlling the catalyst. Phys. Chem. Chem. Phys. 18, 9161–9166 (2016).
water flow rate from 1 to 20 μl/min and fine-­tuning the gas flow 16. J. Nash, X. Yang, J. Anibal, J. Wang, Y. Yan, B. Xu, Electrochemical nitrogen reduction
from 5 to 50 gallons per hour. Two environmental conditions, relative reaction on noble metal catalysts in proton and hydroxide exchange membrane
electrolyzers. J. Electrochem. Soc. 164, 1712–1716 (2017).
humidity and wind speed (mile per hour), can be well simulated 17. J. Wang, L. Yu, L. Hu, G. Chen, H. Xin, X. Feng, Ambient ammonia synthesis via
(relative humidity, 30 to 90%; and wind, 5 to 13 mph) for investigating palladium-­catalyzed electrohydrogenation of dinitrogen at low overpotential. Nat.
their influences on the contact electrification current. Commun. 9, 1795 (2018).
18. X. Fu, J. B. Pedersen, Y. Zhou, M. Saccoccio, S. Li, R. Sažinas, K. Li, S. Z. Andersen, A. Xu,
N. H. Deissler, J. B. V. Mygind, C. Wei, J. Kibsgaard, P. C. K. Vesborg, J. K. Nørskov,
Contract electrification current measurement
I. Chorkendorff, Continuous-­flow electrosynthesis of ammonia by nitrogen reduction and
A picoammeter (Mode 6485, Keithley Instruments, Cleveland, OH, hydrogen oxidation. Science 379, 707–712 (2023).
USA) was used to precisely record the contact electrification current 19. S. Jin, H. Chen, X. Yuan, D. Xing, R. Wang, L. Zhao, D. Zhang, C. Gong, C. Zhu, X. Gao,
generated as follows conditions: (i) interaction between a catalyst Y. Chen, X. Zhang, The spontaneous electron-­mediated redox processes on sprayed
mesh and the spraying water microdroplets with air under varied water microdroplets. JACS Au 3, 1563–1571 (2023).
20. A. J. Colussi, Mechanism of hydrogen peroxide formation on sprayed water
gas and water flow rate (for relative humidity and wind speed simu- microdroplets. J. Am. Chem. Soc. 145, 16315–16317 (2023).
lation); and (ii) interaction between air and spraying water micro- 21. S. Lin, X. Chen, Z. L. Wang, Contact electrification at the liquid-­solid interface. Chem. Rev.
droplets and a catalyst mesh with different Fe3O4-­Nafion composition 122, 5209–5232 (2021).
(for catalyst formula optimization). The location of the catalyst mesh 22. F. Galembeck, L. P. Santos, T. A. L. Burgo, A. Galembeck, The emerging chemistry of
self-­electrified water interfaces. Chem. Soc. Rev. 53, 2578–2602 (2024).
was mounted in front of the sprayer at 10 mm distance. The cathode
23. J. Zhang, X. Liu, H. Liu, Atmospheric nitrogen deposition and its contribution to nitrogen
from the picoammeter is connected to the copper oxide mesh, and removal in aquatic ecosystems. Environ. Sci. Tech. 53, 2034–2043 (2019).
the anode is grounded through the metal tube housing the capillary. 24. L. Liu, X. Huang, M. Li, Chemical transformations and deposition of nitrogen-­containing
The flow rate of water and gas were set at different conditions based aerosols: Implications for air quality and ecosystem health. Atmos. Chem. Phys. 20,
on the relative humidity and wind speed to be simulated. Each mea- 3761–3774 (2020).
25. X. Song, C. Basheer, R. N. Zare, Making ammonia from nitrogen and water microdroplets.
surement includes 50 datapoints every 0.5 s and automatically re- Proc. Nat. Acad. Sci. U.S.A. 120, 2301206120 (2023).
corded by a self-­written Python program. 26. A. Kumar, V. S. Avadhani, A. Nandy, S. Mondal, B. Pathak, V. K. N. Pavuluri, M. M. Avulapati,
S. Banerjee, Water microdroplets in air: A hitherto unnoticed natural source of nitrogen
oxides. Anal. Chem. 96, 10515–10523 (2024).
27. S. Bose, M. Mofidfar, R. N. Zare, Direct conversion of N2 and air to nitric acid in gas–water
Supplementary Materials
microbubbles. J. Am. Chem. Soc. 146, 27964–27971 (2024).
This PDF file includes:
28. X. Song, C. Basheer, Y. Xia, R. N. Zare, Oxidation of ammonia in water microdroplets
Figs. S1 to S13
produces nitrate and molecular hydrogen. Environ. Sci. Tech. 58, 16196–16203 (2024).
Table S1
29. Y. Wang, C. Wang, M. Li, Y. Yu, B. Zhang, Nitrate electroreduction: Mechanism insight, in
situ characterization, performance evaluation, and challenges. Chem. Soc. Rev. 50,
REFERENCES AND NOTES 6720–6733 (2021).
1. Ammonia production worldwide from 2010 to 2023. [Link] 30. P. L. Searle, The Berthelot or indophenol reaction and its use in the analytical chemistry of
statistics/1266378/global-­ammonia-­production/. Statista (2023) [accessed nitrogen. A review. Analyst 109, 549–568 (1984).
8 August 2024]. 31. B. Chen, Y. Xia, R. He, H. Sang, W. Zhang, J. Li, L. Chen, P. Wang, S. Guo, Y. Yin, L. Hu,
2. J. Lim, C. A. Fernández, S. W. Lee, M. C. Hatzell, Ammonia and nitric acid demands for M. Song, Y. Liang, Y. Wang, G. Jiang, R. N. Zare, Water–solid contact electrification causes
fertilizer use in 2050. ACS Energy Lett. 6, 3676–3685 (2021). hydrogen peroxide production from hydroxyl radical recombination in sprayed
3. A. Yapicioglu, I. Dincer, A review on clean ammonia as a potential fuel for power microdroplets. Proc. Nat. Acad. Sci. U.S.A 119, 2209056119 (2022).
generators. Renew. Sustain. Energy Rev. 103, 96–108 (2019). 32. Y. Xia, J. Li, Y. Zhang, Y. Yin, B. Chen, Y. Liang, G. Jiang, R. N. Zare, Contact between water
4. J. Humphreys, R. Lan, S. Tao, Development and recent progress on ammonia synthesis vapor and silicate surface causes abiotic formation of reactive oxygen species in an
catalysts for Haber–Bosch process. Adv. Energy Sustain. Res. 2, 2000043 (2021). anoxic atmosphere. Proc. Nat. Acad. Sci. U.S.A. 120, e2302014120 (2023).

Song et al., Sci. Adv. 10, eads4443 (2024) 13 December 2024 8 of 9

S c i e n c e A d v a n c e s | R e s e ar c h A r t i c l e

33. J. Li, Y. Xia, X. Song, B. Chen, R. N. Zare, Continuous ammonia synthesis from water and 42. Z. Zhu, Z. Zhu, H. Yuan, Y. Wei, P. Li, P. Zhang, D. Xie, Effects of ammonia nitrogen and
nitrogen via contact electrification. Proc. Nat. Acad. Sci. U.S.A. 121, e2318408121 (2024). sediment nutrient on growth of the submerged plant Vallisneria natans. Clean. (Weinh.)
34. X. Song, C. Basheer, Y. Xia, J. Li, I. Abdulazeez, A. A. Al-­Saadi, M. Mofidfar, M. A. Suliman, 43, 1653–1659 (2015).
R. N. Zare, One-­step formation of urea from carbon dioxide and nitrogen using water
microdroplets. J. Am. Chem. Soc. 145, 25910–25916 (2023). Acknowledgments
35. N. Salmon, R. Bañares-­Alcántara, Offshore green ammonia synthesis. Nat. Synth. 2, Funding: This work was supported by the Air Force Office of Scientific Research through the
604–611 (2023). Multidisciplinary University Research Initiative program (AFOSR FA9550-­21-­1-­0170) (R.N.Z.),
36. S.-­X. Li, Z.-­H. Wang, B. A. Stewart, Responses of crop plants to ammonium and nitrate N. Deanship of Research Oversight and Coordination at KFUPM (ER221003) (C.B.), and KFUPM
Adv. Agron. 118, 205–397 (2013). International Summer Research Program (ISP23209) (C.B.). Author contributions:
37. D. T. Britto, H. J. Kronzucker, NH4+ toxicity in higher plants: A critical review. J. Plant Conceptualization: X.S., C.B., and R.N.Z. Methodology: X.S., C.B., and J.X. Investigation: X.S., C.B.,
Physiol. 159, 567–584 (2002). and J.X. Visualization: X.S. and J.X. Supervision: R.N.Z. and C.B. Writing–original draft: X.S. and
38. C. Frerichs, D. Daum, A. S. Pacholski, Ammonia and ammonium exposure of basil C.B. Writing–review and editing: C.B. and R.N.Z. Competing interests: For R.N.Z., C.B., and X.S.,
(Ocimum basilicum L.) growing in an organically fertilized peat substrate and strategies to a patent disclosure has been made to the Stanford Office of Technology Licensing: Expedited
mitigate related harmful impacts on plant growth. Front. Plant Sci. 10, 1696 (2020). chemical reactions at curved microscale interfaces between water and a hydrophobic
39. A. J. P. Smolders, C. den Hartog, C. B. L. van Gestel, J. G. M. Roelofs, The effects of medium. PCT application number PCT/US2024/012974 filed 25 January 2024. The other
ammonium on growth, accumulation of free amino acids and nutritional status of young authors declare that they have no competing interests. Data and materials availability: All
phosphorus deficient Stratiotes aloides plants. Aquat. Bot. 53, 85–96 (1996). data needed to evaluate the conclusions in the paper are present in the paper and/or the
40. S. Shengqi, Y. Zhou, J. G. Qin, W. Wang, W. Yao, L. Song, Physiological responses of Egeria Supplementary Materials.

Downloaded from [Link] at Indian Institute of Technology, Madras on April 23, 2025
densa to high ammonium concentration and nitrogen deficiency. Chemosphere 86,
538–545 (2012). Submitted 13 August 2024
41. H. Chen, Y. Jia, H. Xu, Y. Wang, Y. Zhou, Z. Huang, L. Yang, Y. Li, L.-­S. Chen, J. Guo, Accepted 5 November 2024
Ammonium nutrition inhibits plant growth and nitrogen uptake in citrus seedlings. Sci. Published 13 December 2024
Hortic. 272, 109526 (2020). 10.1126/sciadv.ads4443

Song et al., Sci. Adv. 10, eads4443 (2024) 13 December 2024 9 of 9