Enhancing Hydrogen Production Capability From Urine-Containing Sewage

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Applied Catalysis B: Environment and Energy 353 (2024) 124064

Contents lists available at ScienceDirect

Applied Catalysis B: Environment and Energy


journal homepage: www.elsevier.com/locate/apcatb

Enhancing hydrogen production capability from urine-containing sewage


through optimization of urea oxidation pathways
Yingzhen Zhang a, b, Yonggang Lei a, Yan Yan d, *, Weilong Cai a, b, Jianying Huang b, *,
Yuekun Lai a, b, **, 1, Zhiqun Lin c, *
a
Qingyuan Innovation Laboratory, Quanzhou 362801, PR China
b
National Engineering Research Center of Chemical Fertilizer Catalyst (NERC-CFC), College of Chemical Engineering, Fuzhou University, Fuzhou 350116, PR China
c
Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore 117585, Singapore
d
School of Chemistry and Chemical Engineering, Anhui University of Technology, Ma’anshan 243002, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: The electrochemical urea oxidation reaction (UOR) represents a promising route to sustainable hydrogen pro­
Urea oxidation reaction duction and reuse of urea-containing sewage. However, the efficiency of UOR is hindered by the dehydroge­
Fe-Ni3S2@NiSe2 nation of intermediate *CONH2NH and the conversion of toxic intermediate the *CO. Herein, we report a robust
Selectivity
strategy to elevate UOR performance by introducing iron (Fe) atoms into the Ni3S2@NiSe2 heterojunctions
Hydrogen
Sewage
(denoted Fe-Ni3S2@NiSe2). The Fe-Ni3S2@NiSe2 exhibits remarkable selectivity and electrocatalytic activity
towards UOR, attributed to its reconstruction into Fe-NiOOH species during UOR process, as confirmed by in-situ
Raman technology. Utilizing Fe-Ni3S2@NiSe2 as both the cathode and anode in a single-chamber electrolytic cell,
the hydrogen production rate reaches 588.4 μmol h− 1 in simulated urea-containing sewage and 432.1 μmol h− 1
in actual human urine, respectively. Notably, in both scenarios, no oxygen product is detected, and the hydrogen
production efficiency surpasses that of traditional water splitting by 5.8-fold and 4.3-fold, respectively. In-situ
infrared spectroscopy study reveals that the UOR process involves the cleavage of C-N bond and the generation of
CO2. Density functional theory calculations further signifies that the incorporation of Fe facilitates the dehy­
drogenation of *CONH2NH intermediates, strengthens the d-p hybridization, and weakens O-H bonds, thereby
resulting in reduced energy barriers for UOR. Our strategy holds promise for efficient hydrogen production from
sewage via UOR, offering potential implications for wastewater treatment and clean energy generation.

1. Introduction resulting in 69.9 % energy savings in hydrogen production through


water electrolysis ((1.23–0.37)/1.23 = 69.9 %). The UOR coupled with
The limitations and environmental concerns associated with con­ HER involves two half reactions [6], represented by the following
ventional fossil fuels have spurred the advancement of clean and sus­ chemical reaction [7,8]:
tainable energy sources [1,2]. Among them, hydrogen stands out as a
highly promising clean energy option; however, its production is hin­ Anode: CO(NH2)2 + 6OH‾ → N2 + 5H2O + CO2 + 6e‾; Eθ = − 0.46 V (1)
dered by the kinetically sluggish oxygen evolution reaction (OER) dur­ Cathode: 6H2O + 6e‾ → 3H2 + 6OH‾; Eθ = − 0.83 V (2)
ing water electrolysis at the anode [3]. Notably, urea, a prevalent
pollutant presents in various wastewater streams (e.g., industrial, agri­ Overall: CO(NH2)2 + H2O → CO2 + 3H2 + N2; E = 0.37V θ
(3)
cultural, and municipal wastewater) [4], exhibits a significantly lower
However, the electrochemical UOR is a complex six-electron process
theoretical potential for urea oxidation reaction (UOR, 0.37 V)
involving the generation and desorption of multiple intermediates [9,
compared to OER (1.23 V) [5]. Theoretically, replacing OER with UOR
10], leading to unsatisfactory dynamics. Non-noble metal Ni-based
and coupling the latter with hydrogen evolution reaction (HER) could
chalcogenide electrocatalysts [11–13] possess distinct electronic

* Corresponding authors.
** Corresponding author at: Qingyuan Innovation Laboratory, Quanzhou 362801, PR China.
E-mail addresses: [email protected] (Y. Yan), [email protected] (J. Huang), [email protected] (Y. Lai), [email protected] (Z. Lin).
1
orcid.org/0000-0003-4100-510X

https://doi.org/10.1016/j.apcatb.2024.124064
Received 20 February 2024; Received in revised form 28 March 2024; Accepted 8 April 2024
Available online 14 April 2024
0926-3373/© 2024 Elsevier B.V. All rights reserved.
Y. Zhang et al. Applied Catalysis B: Environment and Energy 353 (2024) 124064

structures and stability, displaying promising electrocatalytic perfor­ 2.3. Characterization


mance for water splitting [14,15] and oxidation reaction of various
nucleophiles (e.g., urea [16], amine [17], etc.). Moreover, diverse The morphology of the as-prepared self-supporting electrodes were
strategies have been employed to enhance their performance, such as imaged using a Zeiss Sigma 300 field emission scanning electron mi­
defect engineering and heteroatom doping or substitution, aiming at croscope (FESEM). Transmission electron microscopy (TEM) images of
optimizing the catalyst surface’s electronic structure and adsorption electrocatalyst was taken using FEI Tecnai-G2-F20 s-twin with an
energy of intermediates [18–20]. Among these strategies, the doping of accelerating voltage of 200 kV. X-ray diffraction (XRD) patterns were
metal elements close to Ni [21,22] into nanostructured transition metal obtained by employing X′Pert3 Powder diffractometer with Cu Kα ra­
sulfide has proven effective in augmenting the electrochemically active diation that is operated at 40 kV and 40 mA. X-ray photoelectron
surface area and electron transfer capability. Notably, a grand challenge spectroscopy (XPS) spectra were attained by a K-Alpha+ instrument
lies in the conversion capability of the CO* intermediate during UOR (Thermo Fisher Scientific), applying a micro-focused, monochromatic
process. Insufficient adsorption and desorption capability on the catalyst Al-Kα X-ray source with 30–500 µm spot size.
surface could lead to active center poisoning and reduced reaction ef­
ficiency, thereby impacting catalytic stability. 2.3.1. In-situ Raman study
Herein, we report a facile strategy to markedly enhance hydrogen In-situ Raman study was carried out using confocal Raman micro­
production efficiency in UOR-assisted water electrolysis by introducing scope (DXR2xi, Thermo Fisher Scientific, 532 nm laser) under different
Fe to promote urea decomposition. Specifically, iron-doped Ni3S2@­ potentials by electrochemical workstation (Versastat 3). The electrolytic
NiSe2 nanocomposites (denoted Fe-Ni3S2@NiSe2) are crafted via an in- cell was homemade with Teflon shell and quartz glass plate. All elec­
situ growth route and employed as self-supporting electrodes. Notably, trochemical tests were performed with a three-electrode configuration,
the introduction of Fe induces morphological and electronic structure where the as-synthesized Fe-Ni3S2@NiSe2, Ag/AgCl electrode, and
changes in Ni3S2@NiSe2 heterojunctions, resulting in an expanded platinum wire are used as the working electrode, reference electrode,
electrochemically active surface area and thus enhanced UOR perfor­ and counter electrode, respectively. The chronoamperometry curves
mance and hydrogen production capacity in urea-containing waste­ were conducted from OCP to 1.60 V vs. RHE.
water. Capitalizing on Fe-Ni3S2@NiSe2 nanocomposites as both cathode
and the anode, hydrogen production rates of 588.4 μmol h− 1 and 432.1 2.3.2. In-situ fourier transform infrared (FTIR) spectroscopy
μmol h− 1 are attained in 1.0 M KOH electrolyte containing 0.33 M urea A Perkin Elmer Spectrum 3 FTIR spectrometer equipped with a
and when using human urine as electrolyte, respectively. No oxygen mercury cadmium telluride detector cooled with liquid nitrogen was
product is detected in both electrolytes. The successful suppression of employed for the in-situ FTIR study. Infrared reflection-absorption
the undesired OER process in urea-containing media underscores the configuration was adopted. Real-time IR spectra was continuously
effectiveness of this strategy for efficient hydrogen production. Impor­ collected by chronoamperometry from OCP to 1.6 V in 1.0 M KOH with
tantly, in-situ Raman, in-situ infrared spectroscopy, and density func­ 0.33 M urea. The spectral resolution is 8 cm− 1 with 44 scans per spec­
tional theory (DFT) calculations were leveraged to comprehensively trum (a collection duration of 30 s).
elucidate the UOR mechanism, revealing that the electrocatalyst un­
dergoes surface reconstruction during electrochemical processes and the 2.4. Electrochemical measurement
introduction of Fe facilitates the optimization of the adsorption and
desorption capabilities of key intermediates on the active centers. Our All electrochemical measurements, except EIS, were performed in a
study holds significant implications for the sustainable utilization of three-electrode system using an electrochemical workstation (Versastat
urea-containing wastewater as a valuable resource for clean hydrogen 3), where the as-synthesized self-supporting electrode, Pt plate and Hg/
production. As such, it contributes to the development of a more envi­ HgO electrode are used as the working electrode, counter electrode and
ronmentally friendly and sustainable energy landscape. reference electrode, respectively.
The Nernst equation is applied to convert potential vs. Hg/HgO
2. Experimental section electrode to potential vs. reversible hydrogen electrode (RHE):

ERHE = EHg/HgO + 0.0059 × pH + 0.098 [23,24] (4)


2.1. Materials
where the ERHE is the potential vs. RHE and EHg/HgO is the potential vs.
Nickel(II) sulfate hexahydrate (NiSO4⋅6 H2O, AR, Aladdin), iron(III) Hg/HgO electrode. 1.0 M KOH with and without 0.33 M urea solution
nitrate nonahydrate (Fe(NO3)3⋅9 H2O, 98.0 %, Damas-beta), selenium were used as respective electrolyte. Linear sweep voltammetry (LSV)
powder (Se, 99.99 %, Aladdin), thiourea (CH4N2S, AR, Sinopharm), N, curves were recorded from 0 to 0.8 V (vs. Hg/HgO) at a scan rate of
N-dimethylformamide (DMF, AR, Sinopharm) and hydrazine hydrate 5 mV s− 1. Operando EIS was conducted over a frequency range from
(N2H4⋅H2O, 85.0 %, Sinopharm) were utilized without any further pu­ 10− 2 to 105 Hz with AC amplitude of 10 mV by ModuLab XM electro­
rification. Nickel foam (NF, thickness: 2 mm) was used as self-standing chemical system (Solartron Analytical).
electrode substrate for electrodeposition.
2.4.1. Faradic efficiency for UOR
2.2. Material preparation The Faradic efficiency (FE) of the Fe-Ni3S2@NiSe2 for UOR was
calculated using the following equations [25]:
Depositing NiSe2 on the surface of nickel foam (NF) by hydrother­
mal. Firstly, NF (4*6 cm2) was cleaned by 3.0 M HCl, ethanol and H2O.
IUOR
FE = × 100% (5)
Secondly, 100 mL DMF, 0.84 mL hydrazine and 3.75 mmol Se, was I
transfer into a 200 mL Teflon-lined stainless autoclave and heated at 180 IUOR = I − IOER (6)

C for 1 h. NiSe2 obtained was washed by water and ethanol, and vac­
uum dried at 60 ◦ C. where, I, IOER, and IUOR represent the current recorded at different po­
Fe-doped Ni3S2 on NiSe2 was crafted via water bath method. tential in the presence of urea, the current acquired without urea, and
Immersing NiSe2 in solution containing 160 mM NiSO4⋅6 H2O, 160 mM the current originated from urea oxidation, respectively.
Fe(NO3)3⋅9 H2O and 90 mM thiourea, and heated at 70 ◦ C for 30 min.
Washed several times with water, and vacuum dried at 60 ◦ C to yield Fe
Ni3S2@NiSe2.

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Y. Zhang et al. Applied Catalysis B: Environment and Energy 353 (2024) 124064

2.4.2. Apparent electrochemical activation energy (Ea) 2.5. DFT calculation


The temperature-dependent measurement was performed in a ther­
mostatic water bath. The apparent electrochemical activation energy Density functional theory (DFT) calculations were performed by
(Ea) for UOR can be determined by the Arrhenius equation [26]: employing the generalized gradient approximation with the Perdew-
Burke-Ernzerhof (PBE) functional [27], as implemented in Vienna ab
∂(logik ) Ea
|= (7) initio Simulation Package (VASP) [28]. All spin-polarized calculations
∂(1/T) 2.3R
were performed using the projector augmented wave (PAW) pseudo­
potential [29,30]. The force and energy convergence tolerance were set
where ik is the kinetic current at a potential of 1.70 V (vs. RHE) at
at 0.02 eV and 10− 5 eV for geometry optimization, respectively. For all
different temperatures, T is the temperature, and R is the universal gas
slab model DFT calculations, a 3 × 3 × 1 Monkhorst-Pack k-point grid
constant. The Arrhenius plots were obtained and the Ea was extracted
was used for the slab model Brillouin zone integration. Slabs were
from the slop of the plots.
separated by 15 Å of vacuum to minimize spurious self-interactions
between periodic images in the z-direction. DFT dispersion correction
2.4.3. Product detection
(DFT-D3) method was used to treat van der Waals interactions. Free
To collect and analyze the emission gas during water splitting and in
energies are approximated as follows:
UOR&HER system, the gas was collected from single-chamber electro­
lytic cell in a continuous running. The details are as follows: (1) the air ΔG = EDFT + ΔZPE –TΔS (8)
was purged with high-purity Ar gas prior to experiment. (2) in an out­
door environment, solar panel was illuminated by sunlight to generate where EDFT and ΔZPE are the total and zero-point electronic energy
electricity as the renewable electrical energy supply source (Video S1). calculated, respectively, by DFT, and TΔS is entropic contribution (only
(3) Gas products were detected by gas chromatography (Shimadzu GC- taken into account for gas phase species and intermediate species).
2014). We consider the UOR process following the elementary steps as
Supplementary material related to this article can be found online at depicted in Eqs. (9)-(15):
doi:10.1016/j.apcatb.2024.124064.
ΔG1: CO(NH2)2*+ OH- → CO(NH2NH)* +H2O+e- (9)

ΔG2: CO(NH2NH)* + OH- → CONH2N* +H2O+e- (10)

Fig. 1. (a) Schematic illustration of Fe-Ni3S2@NiSe2. SEM images of (b) Nickle foam (NF), (c) NiSe2, (d) Fe-Ni3S2@NiSe2. (e) EDS-mapping of Fe-Ni3S2@NiSe2.
HRTEM images of (f) Ni3S2@NiSe2 and (g-h) Fe-Ni3S2@NiSe2, respectively.

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Y. Zhang et al. Applied Catalysis B: Environment and Energy 353 (2024) 124064

ΔG3: CO(NH2N)* + OH- → CONHN* +H2O+e- (11) heterojunction presents clear lattice fringes (Fig. 1f) with the lattice
spacing of 0.269 nm and 0.287 nm, corresponding to the (210) crystal
ΔG4: CONHN* + OH- →⋅CON2* +H2O+e- (12) lattice of NiSe2 [31] and the (110) crystal lattice of Ni3S2 [32], respec­
tively. It is notable that the microstructure of Fe-Ni3S2@NiSe2 appears
ΔG5: CON2* → CO* +N2 (13) more fluffy (Fig. 1g), and the lattice arrangement of Ni3S2@NiSe2 be­
comes disordered (Fig. 1h) after the introduction of Fe elements. Such
-
ΔG6: CO* + OH → COOH* + e -
(14)
disorder may be related to the change of intrinsic electric field of
-
ΔG7: COOH* + OH → CO2* +H2O+e -
(15) Ni3S2@NiSe2, which was caused by the introduction of Fe atoms [33,
34]. It will be further corroborated in the XPS study.
where * represents an active site on the surface of catalyst. X-ray diffraction (XRD) was used to evaluate crystalline phase of the
as-synthesized Fe-Ni3S2@NiSe2 electrocatalysts. As shown in Fig. 2a, NF
3. Results and discussion substrate has three Ni characteristic peaks at 2θ of 44.7◦ , 52.1◦ and
76.6◦ , ascribed to the (111), (200) and (220) planes, respectively (PDF
3.1. Characterizations of as-synthesized catalysts No. 04–0850) [18,35]. After NiSe2 was deposited over the NF surface,
XRD peaks at 2θ of 30.2◦ , 33.3◦ , 37.1◦ , 50.6◦ , 55.7◦ , 58.0, 61.9◦ and
Fig. 1a depicts the synthesis schematic of Fe-Ni3S2@NiSe2 self- 70.2◦ were observed, corresponding to the (200), (210), (211), (311),
supporting electrocatalysts. Firstly, commercial nickel foam (NF) with (230), (321), (400) and (420) planes of NiSe2 (PDF No. 41–1495) [36].
a smooth surface (Fig. 1b) was used as a conductive support and Ni Moreover, when Fe-Ni3S2 was deposited on the surface of NF, a set of
source. NiSe2 was in-situ constructed on the surface of NF via a hydro­ XRD peaks at 2θ of 22.2◦ , 31.5◦ , 38.2◦ , 50.4◦ and 55.6◦ were found,
thermal method with N,N-dimethylformamide (DMF) as the solvent and corresponding to the characteristic peaks of (101), (110), (021), (211)
Se powder as the Se source. Subsequently, Fe-doped Ni3S2 was decorated and (300) crystal planes of Ni3S2 (PDF No. 44–1418) (Figure S2) [37].
on the surface of NiSe2 via water bath heating by employing thiourea as Importantly, when Fe-Ni3S2 was further deposited over NiSe2-coated NF
the sulfur source, hexahydrate nickel sulfate as the nickel source, and (i.e., forming Fe-Ni3S2@NiSe2), the characteristic peaks of both Fe-Ni3S2
hexahydrate iron nitrate as the iron source. Finally, Fe-Ni3S2@NiSe2 and NiSe2 can be seen, substantiating the successful preparation of
nanocomposites were yielded. The SEM measurements revealed that Fe-Ni3S2@NiSe2 electrocatalysts.
NiSe2 has a stalactite-like morphology (Fig. 1c), and Ni3S2@NiSe2 X-ray photoelectron spectroscopy (XPS) was then utilized to analyze
nanocomposites display a cluster-like morphology (Figure S1), while Fe- surface chemical composition and electronic state of Fe-Ni3S2@NiSe2.
Ni3S2@NiSe2 nanocomposites display a mossy-like morphology The Ni 2p spectrum of Fe-Ni3S2@NiSe2 exhibits two main peaks at
(Fig. 1d). The energy dispersive spectroscopy (EDS) mapping shows that 855.40 eV (Ni2+ 2p3/2) and 873.24 eV (Ni2+ 2p1/2), along with two
abundant Ni, Se and S elements were uniformly distributed on the NF satellite peaks (Fig. 2b) [16,38]. Compared to the pure Ni3S2@NiSe2, Fe
substrate, with a small amount of Fe elements evenly covering the sur­ doping induces a negative shift in the binding energy of the Ni 2p or­
face (Fig. 1e). The HR-TEM image shows that the Ni3S2@NiSe2 bitals. This is attributed to the introduction of additional electrons by Fe

Fig. 2. (a) XRD paterns. High-resolution XPS spectra of (b) Ni 2p, (c) Se 3d, (d) S 2p and (e) Fe 2p, respectively. (f) XPS survery of Fe-Ni3S2@NiSe2.

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Y. Zhang et al. Applied Catalysis B: Environment and Energy 353 (2024) 124064

doping, thereby increasing the electron density around the Ni atoms, electrocatalysts (Figure S4). Fig. 3a shows that Fe-Ni3S2@NiSe2 has an
leading to a decrease in the binding energy of the Ni 2p orbitals. The Se ECSA of 192.8 cm2, which is larger than that of Ni3S2@NiSe2
3d spectrum shows two fitted peaks at 54.62 eV and 56.40 eV, corre­ (137.8 cm2), NiSe2 (110.3 cm2) and Fe-NiSe2 (76.8 cm2). To further
sponding to the spin-orbits 3d5/2 and 3d3/2 of Se, respectively, and a investigate the number of active sites in the as-synthesized electro­
characteristic peak ascribed to selenate was also observed at 58.75 eV catalysts, pulsed I-t measurement [41] was performed by calculating the
(Fig. 2c) [39]. The S 2p spectrum displays two fitted peaks at 162.03 eV stored passing charge at 1.0 V, as shown in the cathodic I-t curve
and 164.13 eV, assigned to the spin orbits 3d3/2 and 3d1/2 of S 2p, (Fig. 3b). The results indicate that Fe-Ni3S2@NiSe2 manifests a higher
respectively, which are characteristic peaks of the Ni-S bond, and the passing charge (1.55 C) compared to the pristine Ni3S2@NiSe2 sample
peak at 168.52 eV can be assigned to sulfate (Fig. 2d) [40]. The Fe XPS (0.63 C) under the same measurement condition, suggesting that Fe
spectrum shows that the Fe 2p3/2 peak could be divided into two peaks doping promotes the exposure of active sites, which is in good agree­
centered at 711.11 eV and 714.14 eV, corresponding to Fe2+ and Fe3+ ment with the ECSA results. Thus, Fe-Ni3S2@NiSe2 was chosen as a
[10], respectively. The Fe 2p1/2 peak is located at 724.54 eV, attributing representative sample to further investigate its electrocatalytic proper­
to Fe2+ (Fig. 2e) [40]. Fe-Ni3S2@NiSe2 consists of Fe, Ni, S, Se and O ties and reaction mechanism.
elements (Fig. 2f). The UOR was carried out in 1.0 M KOH containing 0.33 M urea,
where the competing reaction anodic OER may also take place. Linear
3.2. Electrochemical performance characterization sweep voltammetry (LSV) was initially performed to assess the elec­
trocatalytic ability of UOR and OER for Fe-Ni3S2@NiSe2. The potential
The electric double layer capacitance (Cdl) of electrocatalysts was difference between the UOR and OER (ΔE = EUOR-EOER) serves as a
measured in the non-Faradaic current region (Figure S3) and used it to descriptor of the electrocatalyst’s selectivity. The Fe-Ni3S2@NiSe2
calculate the electrochemically active surface area (ECSA) of electrocatalyst exhibits an excellent UOR selectivity (ΔE =162.7 mV)

Fig. 3. (a) Cdl of Fe-Ni3S2@NiSe2, Ni3S2@NiSe2, Fe-NiSe2, and NiSe2. (b) Pulsed I-t curves of Ni3S2@NiSe2 and Fe-Ni3S2@NiSe2, oxidizing the samples at 1.35 V for
150 s, followed by reduction at 1.0 V for 150 s, in 1.0 M KOH. (c) LSV curves. (d) Histogram of Fe-Ni3S2@NiSe2 electrooxidation selectivity for different reactions. (e)
Tafel plots of Fe-Ni3S2@NiSe2 for UOR and OER, respectively. (f) Arrhenius plots infer the activation energy of Fe-Ni3S2@NiSe2 for UOR and OER, respectively. (g)
Arrhenius plots infer the activation energy of Fe-Ni3S2@NiSe2, Ni3S2@NiSe2, Fe-NiSe2, and NiSe2 for UOR. (h) Stability test of Fe-Ni3S2@NiSe2 at j = 50 mA cm− 2 in
1.0 M KOH with 0.33 M urea; insert shows the LSV curves of Fe-Ni3S2@NiSe2 before and after the UOR stability test.

5
Y. Zhang et al. Applied Catalysis B: Environment and Energy 353 (2024) 124064

(Fig. 3c). To better reflect the intrinsic activity of the Fe-Ni3S2@NiSe2, signifies that the presence of urea did not hinder the HER activity and
the ECSA was used to normalize the current density. The UOR exhibited the electrocatalyst was well-suited for dual-function, single-chamber
excellent intrinsic activity (Figure S5). Moreover, the electrocatalyst electrolyzers. To examine the performance of urea oxidation-assisted
also manifests good electrocatalytic selectivity for other small molecules water splitting to produce hydrogen, a single-chamber electrolyzer
(e.g., methanol as in methanol oxidation reaction (MOR) and ammonia was assembled with Fe-Ni3S2@NiSe2 self-supporting electrocatalysts
as in ammonia oxidation reaction (AOR)) (Fig. 3d and Figure S6). functioning as both the cathode and anode (Fig. 4a). To reach a current
Furthermore, the onset potential (Eonset) reflects electrocatalytic density of 100 mA cm− 2, the required voltage was 108.3 mV in 1.0 M
ability of electrocatalyst. As shown in Figure S7, the Eonset for OER was KOH with 0.33 M urea, lower than that in 1.0 M KOH electrolyte
1.52 V in 1.0 M KOH, with a pre-oxidation peak at 1.46 V (due probably (Figure S13). As depicted in Fig. 4b and f, in the urea oxidation-coupled
to the transition of Ni to a higher oxidation state) [20]. Upon the with hydrogen evolution reaction (UOR||HER) system, the hydrogen
addition of urea, a considerable surge in the anodic current was production rate reached 588.4 μmol h− 1. In a human urine environment,
observed, and the Eonset of UOR (Eonset = 1.33 V) is much lower than that the hydrogen production rate was 432.1 μmol h− 1. Notably, the
of OER (Eonset = 1.52 V). Due to the slow kinetics of the OER at low hydrogen production rates in both aforementioned environments are
potentials, the FE of the UOR was higher at low potentials compared to higher than that in water splitting system (HER||OER; 101.8 μmol h− 1).
high potentials. Fe-Ni3S2@NiSe2 exhibits a high FE, remaining close to Moreover, in urea-containing system, almost no oxygen (O2) was
80 % even at an applied potential of 1.45 V vs. RHE (Figure S8). This generated, while 58.2 μmol h− 1 of oxygen was detected in HER||OER
suggests that the Fe-Ni3S2@NiSe2 possesses a favorable electrocatalytic system (in 1.0 M KOH; Fig. 4c and Figure S14-16). It corroborates that
activity for urea oxidation, rendering it a promising catalyst for UOR the substitution of OER with UOR could lead to effective inhibition of O2
under low potential. generation and low-energy-consumption hydrogen production with
Tafel plots is widely used to characterize the kinetic rate of electro­ markedly improved efficiency.
catalytic reactions, where a smaller Tafel slope indicates a more favor­ The reaction kinetics of Fe-Ni3S2@NiSe2 involved in both UOR and
able catalytic reaction [42]. The smaller Tafel slope of Fe-Ni3S2@NiSe2 OER processes were explored by electrochemical impedance spectros­
for UOR (78.7 mV dec− 1) than OER (332.0 mV dec− 1) was observed copy (EIS). The Bode plots depict the phase angle as a function of fre­
(Fig. 3e), insinuating that the reaction kinetics of UOR is much faster quency, where the low-frequency region (10− 1 - 101 Hz) is associated
than that of OER. Furthermore, the Arrhenius plot can be fitted to a with interfacial reactive charge transfer processes (i.e., electrooxidation
straight line, with the slope representing the electrochemical activation reaction of reactants, that is, urea and OH‾ as in this study) [44,45]. As
energy (Ea) [7,43]. The Ea was tested at different temperatures (30, 40, shown in Fig. 4d-e, phase angle in the low-frequency region gradually
50, 60, and 70 ℃) by LSV (Figure S9). In Fig. 3f, the Ea of Fe-Ni3S2@­ decreases with increasing potential, indicating that charge transfer of
NiSe2 was 4.79 and 5.36 kJ mol− 1 during UOR and OER processes, the interface reaction was accelerated, which favors the thermody­
respectively. The lower Ea for UOR indicates that the energy barrier to be namics of water and urea oxidation reactions [46]. The phase angle
crossed is smaller, and the UOR proceeds faster than OER thermody­ value of Fe-Ni3S2@NiSe2 in 1.0 M KOH with 0.33 M urea was lower than
namically, which is consistent with the Tafel plot results. Additionally, in 1.0 M KOH electrolyte, suggesting that UOR process has a faster ki­
during UOR process, the Ea of Fe-Ni3S2@NiSe2, Ni3S2@NiSe2, Fe-NiSe2 netics. On the other hand, in the high-frequency region (101 - 105 Hz),
and NiSe2 were 4.79, 6.73, 7.07 and 6.48 kJ mol− 1, respectively phase angle is related to electron transfer within electrocatalyst from the
(Fig. 3g), demonstrating that the introduction of Fe into Ni3S2@NiSe2 inner layer to surface,[44] reflecting the properties of electrocatalyst
heterostructure could effectively reduce the Ea of UOR. itself. In the present study, the phase angle in the high frequency region
The electrocatalytic stability was evaluated by chronopotentiometry. did not changed significantly regardless of UOR or OER process, indi­
Fe-Ni3S2@NiSe2 exhibited no obvious potential fluctuation at a current cating that a fast electron transfer [47] and Fe-Ni3S2@NiSe2 possesses a
density of 50 mA cm− 2 during 24 h and 48 h continuous testing in 1.0 M good electrical conductivity. During the OER process, the Nyquist plots
KOH electrolyte (Figure S10), indicating that the electrocatalyst had a show steep straight lines at low potentials (1.30 ~ 1.45 V vs. RHE)
superb electrochemical stability. However, the potential increased (Fig. 4g), which indicates an infinite charge transfer resistance. In the
significantly after 24 h in 1.0 M KOH containing 0.33 M urea. Interest­ urea-containing system, when the applied potential exceeds 1.35 V,
ingly, the potential returned to its original value after the electrolyte was semi-circles are appeared in the Nyquist diagram (Fig. 4h), suggesting
replaced, suggesting that the potential increase was caused by the con­ the occurrence of UOR and accelerated interfacial charge transfer,
sumption of urea in the electrolyte. By replacing the electrolyte, the Fe- further confirming the faster reaction kinetics of UOR over OER.
Ni3S2@NiSe2 maintained an excellent electrocatalytic stability after
168 h of continuous testing for UOR (Fig. 3h), and the potential differ­ 3.3. Investigation of the catalytic mechanism
ence was only 13 mV (before and after long-time stability testing; the
insert in Fig. 3h), which outperforms recently reported self-supported Fig. 5a depicts in-situ Raman investigation into the surface species of
catalysts listed in Table S1. Furthermore, to assess the stability of Fe- Fe-Ni3S2@NiSe2 electrocatalyst during UOR process. At the open circuit
Ni3S2@NiSe2 under industrial conditions, the durability test was con­ potential (OCP), a characteristic peak at 1000 cm− 1 was observed
ducted at 500 mA cm− 2 (a current density consistent with industrial (Fig. 5b), which can be assigned to the C-N bond in urea [48], sub­
requirements) by chronopotentiometry. As shown in Figure S11, with stantiating the adsorption of urea molecules on the catalyst’s surface. As
increasing time, the voltage gradually increased. However, upon the applied voltage was increased from 1.25 V to 1.30 V, two new peaks
replacing the electrolyte with fresh solution, the current density almost at 472 cm− 1 and 559 cm− 1 were emerged, corresponding to the NiIII-O
entirely reverted to its initial level. This observation could be attributed bending vibration [49] and O-NiIII-O stretching vibration [50,51],
to the consumption of urea (a reactant during the electrolysis process), respectively. This finding provide evidence that the surface of
leading to a decrease in urea concentration near the electrode and Fe-Ni3S2@NiSe2 was reconstructed into Fe-NiOOH during UOR process.
hindering mass transfer efficiency. This issue was effectively addressed After the UOR process, Fe-Ni3S2@NiSe2 underwent significant
by replacing the electrolyte with fresh solution. Additionally, after 5 morphological changes (Figure S17), suggesting that the surface of
cycles, the catalytic performance remained nearly unchanged from the electrocatalysts was restructured during the electrochemical process.
initial state, demonstrating the excellent electrochemical stability of Fe- Additionally, the XRD study revealed that the crystal structure of elec­
Ni3S2@NiSe2. trocatalyst was markedly altered during UOR process, where two new
The Fe-Ni3S2@NiSe2 electrocatalyst also manifests a good HER ac­ characteristic peaks at 2θ = 43.1◦ and 48.6◦ were seen, which can be
tivity in 1.0 M KOH (Figure S12), where the addition of 0.33 M urea to assigned to NiOOH (Figure S18) [52]. This finding further confirms that
the electrolyte did not significantly affect the HER performance. This Fe-Ni3S2@NiSe2 was reconstructed during UOR process, and its

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Y. Zhang et al. Applied Catalysis B: Environment and Energy 353 (2024) 124064

Fig. 4. Electrocatalytic performance test of Fe-Ni3S2@NiSe2. (a) LSV curves in 1.0 M KOH with and without 0.33 M urea. (b) H2 and (c) O2 products at E = 1.6 V
from 1.0 M KOH, 1.0 M KOH with 0.33 M urea, and 1.0 M KOH with human urine. (d-e) Bode plots of Fe-Ni3S2@NiSe2 for (d) the UOR and (e) the OER process at
various voltages. (f) Digital photograph of a two-electrode cell for the HER||UOR system. (g-h) Nyquist plots of Fe-Ni3S2@NiSe2 for (g) OER and (h) UOR process at
various voltages.

morphology change was caused by this reconstruction during the elec­ to monitor the pivotal species during UOR process. A positive absorption
trochemical process. Furthermore, XPS spectra of Fe-Ni3S2@NiSe2 peak indicates accumulation of species on the catalyst surface, whereas a
before and after UOR process are shown in Figure S19. After UOR pro­ negative peak suggests consumption of species on the catalyst surface
cess, the Ni 2p spin-orbit was split into Ni 2p3/2 and Ni 2p1/2. The Ni [56]. For Ni3S2@NiSe2, with an increase in the applied potential, the
2p3/2 peaks at 855.28 eV and 856.44 eV can be ascribed to Ni2+ and absorption peaks were gradually sharpened at 1270 cm− 1 (Fig. 5d),
Ni3+, while the Ni 2p1/2 peaks at 872.96 eV and 874.86 eV can be corresponding to the C– –O bond in *COOH species (where * represents
attributed to Ni2+ and Ni3+ [53–55], respectively. In addition, the peaks the active site). At 1640 and 2918 cm− 1, the bending vibration of O-H
at 861.19 eV and 879.22 eV correspond to the shakeup satellite peak bond become stronger with the increase of applied potential, which
(Figure S19 a). Compared with pristine Fe-Ni3S2@NiSe2, Ni 2p displays involves the fracturing of O-H bond in *COOH [57]. When the applied
a pair of peaks of Ni3+, confirming the formation of NiOOH during UOR potential is over 1.50 V, a peak at 1508 cm− 1 was detected, which is due
process. Furthermore, an analysis of the Fe 2p spin orbitals before and to the cleavage of C-N bond in *O– –C-(N)2 species [45]. Moreover, an
after participating in the UOR process revealed a new characteristic peak absorption peak owing to the stretching vibration of the N-H bond was
near a binding energy of 707.11 eV, corresponding to 0-valent Fe. This found at 1106 cm− 1, which is related to urea dehydrogenation during
indicates that Fe acts as an electron acceptor, receiving electrons from UOR process [58]. Furthermore, the above observation also illustrates
Ni, facilitating the oxidation of Ni2+ to high-valent Ni species (NiIIIOOH) that urea preferentially undergoes the dehydrogenation process rather
while being reduced to Fe0 itself. These results are consistent with the than breaking the C-N bond. After the applied potential is higher than
XRD and in-situ Raman studies, substantiating that Fe-Ni3S2@NiSe2 1.55 V, two peaks at 2340 and 2851 cm− 1 associated with CO2- 3 were
undergoes surface reconstruction during UOR process to form functional seen [59], which are attributed to the dissolution of the CO2 product in
oxidation state of Fe-doping Ni (oxy)hydroxides (Fe-NiOOH) species, alkaline solution [60]. In contrast, for Ni3S2@NiSe2 without introducing
which is regarded as the active sites involved in the pathway and Fe atoms, the bending vibration of O-H bond and the stretching vibra­
mechanism of UOR. tions of C– –O bond and C-N bond were weaker compared to
In-situ Fourier transform infrared spectroscopy (FTIR) was employed Fe-Ni3S2@NiSe2 (Figure S20), suggesting that the active center with iron

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Y. Zhang et al. Applied Catalysis B: Environment and Energy 353 (2024) 124064

Fig. 5. (a) Schematic of in-situ Raman setup. (b) In-situ Raman spectra of Fe-Ni3S2@NiSe2 for the UOR process. (c) Pathway of the UOR process. (d) In-situ FTIR
spectra of Fe-Ni3S2@NiSe2 at continuous applied potentials from OCP to 1.60 V. RE, CE, WE, and OCP represent reference electrode, counter electrode, working
electrode, and open circuit potential, respectively.

introduced facilitates the oxidization of urea into the *COOH in­ respectively.
termediates and thus the formation of CO2. On the basis of the results As shown in Fig. 6d, urea dissociation is proposed to consist of four
discussed above, a possible pathway of UOR process was proposed, steps, namely, urea adsorption (*CO(NH2)2), dehydrogenation
involving (1) the adsorption of urea on the surface of electrocatalyst, (2) (*CONH2NH → *CONH2N → *CONHN), N-N coupling (*CON2 →
urea dehydrogenation, (3) breaking of C-N bond, and (4) formation of CO*+*N2), and CO2 desorption (*CO → *COOH → *CO2). Specifically,
CO2, as depicted in Fig. 5c. the potential-determining step (PDS) of Fe-NiOOH is the CO2 desorption
To decipher the origin of the superior UOR performance rendered by with a corresponding energy barrier of 2.86 eV (Fig. 6e), which is lower
doping Fe atoms in Ni3S2@NiSe2, the DFT calculation was exploited to than that of NiOOH (3.11 eV). Furthermore, the O-H bond in *COOH
analyze the change of energy barriers and electronic structure induced intermediate was found to be weaker on the Fe-NiOOH surface, as evi­
by Fe doping. Based on in-situ Raman, XPS and XRD results, after the denced by crystal orbital Hamilton populations (COHP) analysis, further
UOR process, the Fe-Ni3S2/NiSe2 heterojunction experienced surface suggesting easier cleavage of the O-H bond during the PDS process. The
reconstruction into high-valent γ-NiOOH, which was considered to be projected COHP profiles (pCOHP) show the bonding (-pCOHP > 0) and
real active sites for UOR. Thus, γ-NiOOH with low-index surfaces (100) anti-bonding (-pCOHP < 0) interaction of O-H bond in COOH adsorbed
was chosen as the theoretical model to represent Ni3S2@NiSe2 (Fig. 6a). on Fe-NiOOH and NiOOH surface, respectively. Integrating the pCOHP
For Fe-Ni3S2@NiSe2, the Ni sites on the surface of NiOOH was replaced to Fermi level (E = 0 eV) gives the ICOHP, which is a measure of bond
by Fe atom (denoted Fe-NiOOH; Fig. 6b). The projected density of states strength [33]. Notably, COOH adsorbed on Fe-NiOOH surface exhibits a
(PDOS) of Fe-NiOOH reveals that the PDOS near the Fermi level (EF) is much lower -ICOHP value (0.0452, in Fig. 6f) of O-H bond than that on
mainly contributed by the Ni 3d, Fe 3d, and O 2p orbitals (Figure S21). NiOOH surface (0.0466, in Figure S24), suggesting easy cleavage of O-H
The PDOS of NiOOH reveals that the PDOS near the Fermi energy (EF) is bond on Fe-NiOOH. Taken together, doping Fe atom in NiOOH
mainly contributed by the Ni 3d, and O 2p orbitals (Figure S22). strengthens the d-p hybridization and weakens the O-H bond of PDS,
Notably, the anti-bonding state of Ni 3d - O 2p hybridization in Fe- thus effectively reducing the PDS of UOR process and resulting in
NiOOH (Fig. 6c) was weaker than that of NiOOH (Figure S23), leading enhanced catalytic activity.
to a strengthened d-p hybridization in Fe-NiOOH, which render the
possibility of enhanced electron transfer and exchange capability to 4. Conclusion
activate and accelerate the UOR process. Moreover, free energy dia­
grams of UOR process were calculated in order to understand the In summary, we developed a viable strategy involving the intro­
intrinsic reactivity of urea dissociation at NiOOH and Fe-NiOOH surface, duction of Fe into the active site of Ni3S2@NiSe2 heterojunction to

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Y. Zhang et al. Applied Catalysis B: Environment and Energy 353 (2024) 124064

Fig. 6. Theoretical model of (a) NiOOH and (b) Fe-NiOOH, respectively. (c) PDOS of Ni 3d and O 2p orbitals in Fe-NiOOH. (d) The pathways of UOR on Fe-NiOOH
and NiOOH, respectively. (e) Gibbs-free-energy of Fe-NiOOH and NiOOH towards UOR. (f) pCOHP of Fe-NiOOH for O-H interaction.

enhance the UOR-assisted HER process for the eco-friendly production also substantiated by in-situ infrared spectroscopy investigation. Overall,
of green hydrogen with low energy consumption. Importantly, as our strategy of introducing Fe atoms into the heterojunction and
revealed by in-situ Raman study, the Fe-Ni3S2@NiSe2 experiences sur­ substituting OER with UOR has greatly amplified the hydrogen pro­
face restructuring into Fe-NiOOH species during the electrochemical duction capacity of the electrolytic process, offering a promising solu­
process, which function as the actual catalytic center for UOR. Utilizing tion for sewage reuse and low-energy-consumption hydrogen
the as-synthesized electrocatalysts as both cathode and anode, a single- production.
chamber electrolytic cell was constructed. The hydrogen production
rates reached 588.4 μmol h− 1 and 432.1 μmol h− 1 in human urine and CRediT authorship contribution statement
1.0 M KOH containing 0.33 M urea as electrolytes, respectively, with no
oxygen products detected. This observation underscores the effective Yingzhen Zhang: Formal analysis, Investigation, Writing–original
suppression of the OER process in the urea-containing electrolyte, draft. Yonggang Lei: Investigation. Yan Yan: DFT calculation. Weilong
highlighting the superior selectivity of Fe-Ni3S2@NiSe2 for UOR. Cai: Investigation. Jianying Huang: Conceptualization, Funding
Furthermore, DFT calculations found that the dehydrogenation of acquisition, Writing–review & editing. Yuekun Lai: Conceptualization,
*CONH2NH and *CONHN species occurs spontaneously, and the barrier Funding acquisition, Writing–review & editing. Zhiqun Lin: Concep­
for CO2 generation is reduced due to the introduction of Fe. This result is tualization, Writing–review & editing.

9
Y. Zhang et al. Applied Catalysis B: Environment and Energy 353 (2024) 124064

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