Supporting Information

Interface Engineering of MoS2@Fe(OH)3 Nanoarray

Heterostucture: Electrodeposition of MoS2@Fe(OH)3 as N2

and H+ Channels for Artificial NH3 Synthesis under Mild

Conditions

Xiaolong Xu,a Xuejing Liu,a Jinxiu Zhao,a Dan Wu,a,c Yu Du,c Tao Yan,b

Nuo Zhang,a Xiang Rena,c,* and Qin Weia,c,*

a
Key Laboratory of Interfacial Reaction & Sensing Analysis in

Universities of Shandong, School of Chemistry and Chemical

Engineering, University of Jinan, Jinan 250022, Shandong, China

b
School of Water Conservancy and Environment, University of Jinan,

Jinan 250022, Shandong, China

c
Collaborative Innovation Center for Green Chemical Manufacturing

and Accurate Detection, Jinan 250022, Shandong, China

Corresponding author

1
Pro. Xiang Ren

Email address: [email protected]

Pro. Qin Wei

Email address: [email protected]

Materials
Anhydrous sodium molybdate (Na2MoO4), sodium nitroprusside
(C5FeN6Na2O2·H2O), ammonium chloride (NH4Cl), and sodium hypochlorite solution
(NaClO) were purchased from Maclean. Thiourea (CH4N2S) and ferric chloride
hexahydrate (FeCl3·6H2O) were purchased from Sinopharm Chemical Reagent Co.,
Ltd. Anhydrous sodium sulfate (Na2SO4) and sodium salicylate (C7H5NaO3) were
purchased from Aladdin. Anhydrous ethanol (C2H5OH) and hydrazine hydrate
(N2H4·H2O) were purchased from Tianjin FuYu Chemical Fine Co., Ltd. Sodium
hydroxide (NaOH) was purchased from Tianjin Damao Chemical Reagent Factory,
and nitric acid (HNO3) and hydrochloric acid (HCl) were purchased from Yantai Far
East Fine Chemical Co., Ltd.
Apparatus
CHI 760D electrochemical workstation obtained from Shanghai Chenhua
Instrument Co., Ltd, China was employed for all electrochemical measurements. X-
ray diffraction (XRD) patterns were acquired by using D8 focus diffractometer
(BLumker AXS, Germany). Transmission electron microscopy (TEM) image was
acquired by a JEOL JEM-2100F TEM (Japan). The absorbance data of
spectrophotometer were measured on TU-1909 spectrophotometer (Beijing Puxi
Instrument Co. Ltd, China).
Preparation of MoS2/CC
The MoS2/CC was prepared by hydrothermal method. Anhydrous sodium
molybdate (0.2086 g) and thiourea (0.3050 g) were added to a clean 50.0 mL beaker,
then 22.0 mL of deionized water was added and magnetically stirred for half an hour

2
to fully dissolve to form a uniform colorless solution. The resulting solution and a
piece of treated carbon cloth (2 × 4 cm) were all transferred to a 50 mL high stainless
steel Teflon-lined autoclave, and kept at 220 °C for 24 hours. After cool to room
temperature, the resulting MoS2/CC was taken out, and washed with ultrapure water
and ethanol, and dried at 60 °C for 2 hours.

Preparation of MoS2@Fe(OH)3/CC
Electrodepositing Fe(OH)3 on MoS2/CC was carried out in a standard three-
electrode electrochemical cell (the obtained MoS 2/CC as working electrode, the
calomel electrode as reference electrode, and the platinum rod electrode as counter
electrode). The electrolyte was 0.1 mol/L ferric chloride solution. The
electrodeposition experiment was carried out by running 4 times CV experiment with
scan rate of 5 mV/s. The potential scan range was −1.0 − 0 V, and every scan time
was 400 s for 20 times. After the deposition was completed, the resulting composite
catalyst (MoS2@Fe(OH)3/CC) was taken out, then washed several times with ethanol
and deionized water, respectively. The Fe(OH) 3 was electrodeposited on MoS 2/CC
successfully for MoS2@Fe(OH)3/CC formation.
Electrochemical Measurements
Before NRR tests, the Nafion membrane was pre-treated by heating in 5% H 2O2
solution and ultrapure water at 80 °C for 1 h, respectively. Electrochemical
measurements were performed with a CHI 660E electrochemical analyzer (CHI
Instruments, Inc., Shanghai) in a standard three-electrode system using
MoS2@Fe(OH)3/CC as working electrode, Ag/AgCl as reference electrode, and
graphite rod as counter electrode. All experiments were carried out at room
temperature (25 °C). For N2 reduction experiments, the 0.1 M Na2SO4 was bubbled
with N2 for 30 min before the measurement.
The following formula was utilized to convert the potential reported in this work to
RHE scale through calibration: E(vs RHE) = E(vs Ag/AgCl)+ 0.197 + 0.059 × pH,
and the polarization curve was the steady-state curve after a few cycles. All

3
electrochemical tests were conducted at 25 °C. During NRR test, 0.1 M Na 2SO4
electrolyte in two chambers of the H-type electrolytic cell was separated by a Nafion
membrane, so that the anode chamber can continuously provide the H + required for
the reaction to the cathode chamber, and the pure High-purity nitrogen was sent to the
cathode chamber for NH3 formation.

Determination of NH3
The produced ammonia was estimated by indophenol blue method by ultraviolet
spectroscopy.[1] In detail, 4 mL electrolyte was removed from the cathodic chamber
and added into 50 μL oxidizing solution containing NaClO (ρCl =4–4.9) and NaOH
(0.75 M), followed by further adding 500 μL coloring solution containing 0.4 M
C7H5O3Na and 0.32 M NaOH, and 50 μL catalyst solution (0.1 g
Na2[Fe(CN)5NO]·H2O diluted to 10 mL with deionized water) in turn. After standing
at 25 °C for 2 h, the UV-Vis absorption spectrum was measured. The concentration of
indophenol blue was determined using the absorbance at a wavelength of 655 nm. In
this study, a concentration-absorbance curve was obtained using a standard
ammonium chloride solution firstly. The fitted curve (y = 0.33x+0.068, R2=0.999)
indicates a good linear relationship between the absorbance value and the NH 3
concentration. Next, electrolyte was obtained from the electrochemical reaction
cathode vessel for UV-Vis spectrometry.
The rate of NH3 yield was calculated using the following formula
NH3 yield rate=(cNH3 × V) / (17 × t × A)
Where cNH3 is the measured NH3 concentration; V is the volume of the electrolyte; t is
the reduction reaction time; and A is the geometric area of the cathode (0.5 × 0.5
cm2).
Determination of N2H4
The possible by-product N2H4 was estimated by Watt and Chrisp method. [2] A
mixture of C9H11NO (5.99 g), HCl (concentrated solution, 30 mL), and C 2H5OH (300
mL) was used as a color developer. The calibration curve was drawn as follows. A
series of 5 mL standard N2H4 solutions were prepared. The N2H4 concentrations in 0.1
4
M Na2SO4 were 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0 µg mL -1, respectively, and were mixed
with the 5 mL color reagents prepared above. After the mixed solution was
sufficiently stirred at room temperature for 10 minutes, the absorbance of the
resulting solution was measured at 455 nm, and the yield of N 2H4 was estimated from
the standard curve made. The calibration curve shows that the absorbance and
N2H4·H2O concentration (y = 0.653x + 0034, R2 = 0.999) have a good linear
relationship through three independent calibrations.
Determination of FE: Since there were three electron transfers in the nitrogen
reduction reaction, the formula for measuring FE in 0.1M Na 2SO4 electrolyte was as
follows:
FE = 3F × cNH3 × V / 17 × Q
Where F is the Faraday constant and Q is the amount of electricity applied.

Computational methods and details

All spin-polarized DFT calculations were performed using the Vienna Ab-initio
Simulation Package (VASP).[3,4] The interaction between ion core and valence
electrons was described by the projector-augmented wave method (PAW).[5] The
exchange-correlation energy was calculated under the generalized gradient
approximation (GGA) with Perdew-Burke-Ernzerhof (PBE).[6] The cutoff of kinetic
energy of 600 eV and the k-points of 3×3×1 were tested to be sufficient for
convergence. The vacuum layer of 15 Å thickness was set to avoid the periodic
interaction and the atoms in the bottom five layers were fixed while other atoms were
relaxed. The atomic positions were optimized until the force on each atom was less
0.03 eV/Å. The constructed catalytic model of the (001) surface of ferrihydrite (Fh)
deposited in MoS2 substrate was based on the experimental characterizations (JCPDS
No. 29-0712) and the theoretical studies.[7, 8] The ferrihydrite has a hexagonal crystal
structure with P63mc space group and the lattice parameters are a=5.93 Å and c=9.13
Å. To account for the strongly correlated d electrons on the iron atoms, we employed
the GGA+U method with an effective value of 3.0 eV. Referring to above reference,

5
we further tested the structural stability of different magnetic orderings, in consistent
with the literature.[7] In the study on the effect of ferrihydrite surface on the N2
electroreduction, Van der Waals (vdW) correction by Grimme’s DFT-D3 method [9]
was further added to describe the non-bonded interaction of the systems. Dipole
correction along the slab normal has also been considered.[10] Based on the
computational hydrogen electrode (CHE) model by Nørskov and coworkers[11], the
Gibbs free energy changes of N2 adsorption and elementary reaction were calculated
by ΔG=ΔE+ΔZPE−TΔS, where ΔE is total energy of the adsorption and elementary
reaction system based on DFT calculations. ΔZPE is the zero point energy (ZPE)
correction, T is the temperature that T=298.15 K is used, and ΔS is the entropy
change. The entropies of gas-phase molecules are obtained from the NIST database.
[12]

6
 ● CC Fe(OH)3/CC
JCPDS:29-0712

Intensity (a.u.)

15 30 45 60
2θ (degree)
Figure S1. XRD pattern for Fe(OH)3/CC.

7
Figure S2. SEM images for MoS2/CC.

8
Figure S3. The cross-section SEM image of MoS2@Fe(OH)3/CC.

9
Figure S4. EDX spectrum of MoS2@Fe(OH)3/CC.

10
Figure S5. SAED pattern taken from MoS2@Fe(OH)3/CC.

11
Figure S6. Optical photograph of the reaction device.

12
Figure S7. Optical photograph of the prepared cathode.

13
Figure S8. (a) After one hour of color development at room temperature, UV−Vis
absorption spectra of various NH3 concentrations. (b) Calibration curve used to
calculate NH3 concentration.

14
 After electrolysis using MoS2@Fe(OH)3/CC
After electrolysis using CC
Before electrolysis

Absorbance

600 650 700 750 800

Wavelength (nm)
Figure S9. UV−Vis absorption spectra of the 0.1 M Na2SO4 electrolyte (after
charging at −0.45 V for 2 h in 0.1 M Na2SO4) after incubated with NH3 color agent
for 1 h under ambient conditions.

15
 After electrolysis
Before electrolysis

Absorbance

600 700 800

Wavelength (nm)
Figure S10. UV−Vis absorption spectra of the 0.1 M Na 2SO4 electrolyte stained with
NH3 color agent before and after 2 h electrolysis at −0.45 V vs. RHE in N 2
atmosphere on the MoS2@Fe(OH)3/CC electrode at open-circuit potential under
ambient conditions.

16
 Before electrolysis
After electrolysis

Absorbance

600 700 800

Wavelength (nm)
Figure S11. UV−Vis absorption spectra of the 0.1 M Na 2SO4 electrolyte stained with
NH3 color agent before and after 2 h electrolysis at −0.45 V vs. RHE in Ar
atmosphereon the MoS2@Fe(OH)3/CC electrode.

17
 0.1 M Na2SO4 after supplying Ar for 0.5 h
0.1 M Na2SO4 after supplying N2 for 0.5 h
0.1 M Na2SO4

Absorbance

600 700 800

Wavelength (nm)
Figure S12. UV−Vis absorption spectra of the 0.1 M Na 2SO4 electrolyte stained with
NH3 color agent before and after continuously supplying N2 or Ar for 0.5 h with no
applied voltage.

18
Figure S13. The change of mNH3 with time under −0.45 V.

19
 6 4
★

Average NH3 yield rate

(˟10-10 mol s-1 cm-2)
3
4

FE (%)
2

2
1

0 0
2h 10 h
Figure S14. NH3 yield rates and FEs after charging at –0.45 V vs. RHE for 2 and 10
h.

20
Figure S15. SEM images of MoS2@Fe(OH)3/CC after stability test in 0.1 M Na2SO4.

21
 MoS2@Fe(OH)3/CC
JCPDS:29-0712
JCPDS:37-1492

Intensity (a.u.)

15 30 45 60
 (degree)
Figure S16. XRD pattern for MoS2@Fe(OH)3/CC after stability test in 0.1 M
Na2SO4.

22
 16

8
j (mA cm-2)
0

-8

-16
0 5 10 15 20 25
Time (h)
Figure S17. Chrono-amperometry curve at potential of –0.45 V vs. RHE using
MoS2@Fe(OH)3/CC catalyst.

23
Figure S18. (a) UV−Vis absorption spectra of various N2H4 concentrations after
incubated for 10 min at room temperature. (b) Calibration curve used for calculation
of N2H4 concentrations.

24
 Before electrolysis
After electrolysis

Absorbance

420 450 480

Wavelength (nm)
Figure S19. UV−Vis absorption spectra of the 0.1 M Na2SO4 electrolyte (after
charging at −0.45 V vs. RHE for 2 h) after incubated for 10 min at room temperature.

25
Figure S20. Free-energy profiles of the NRR at edge sites of MoS 2 (blue dotted line).
The asterisk (*) denotes the adsorption site. (Our Previous Reports: Ref: J. Mater.
Chem. A, 2019, 7, 2524–2528)

26
Figure S21. The optimized configurations and Gibbs free energy changes (ΔG) of N2
adsorption and electroreduction on the Fh(001) and Fh(001)-H 2O surfaces in top
views. The H, N, Fe and O atoms are shown in light pink, blue, brown and red colors,
respectively.

27
Table S1. Comparison of the NH3 electrosynthesis activity for MoS2@Fe(OH)3/CC

in 0.1 M Na2SO4 with other catalysts.

Catalyst Temperature (°C) NH3 yield rate FE Ref.

(%)
−10
MoS2@Fe(OH)3/CC 25 4.23×10 mol s cm
-1 -2
2.76 This work

MoS2/CC 25 8.08×10−11 mol s-1 cm-2 1.17 [13]

MoO3 25 4.80×10–10 mol s–1 cm–2 1.9 [14]

Fe2O3−CNT 25 3.58×10−12 mol s-1 cm-2 0.15 [15]

PEBCD/C 25 2.58×10−11 mol s-1 cm-2 2.85 [16]

TiO2-rGO 25 15.13 µg h−1 mg−1cat. 3.3 [17]

Mo nanofilm 25 3.09×10−11 mol s-1 cm-2 0.72 [18]

Ag 25 2.94×10−14 mol s-1 cm-2 0.46 [19]

MoN 25 3.01 × 10–10 mo1 s–1 cm–2 1.15 [20]

VN 25 8.40 × 10–11 mol s–1 cm–2 2.25 [21]

TiO2 25 9.16 × 10–11 mol s–1 cm–2 2.5 [22]

B4C 25 26.57 μg h–1 mg–1cat. 15.95 [23]

Fe2O3 nanorods 25 15.9 µg h–1 mg–1cat. 0.94 [24]

defect-rich MoS2 25 29.28 µg h–1 mg–1cat. 8.34 [25]

nanoflower
Ag nanosheet 25 4.62 × 10–11 mol s–1 cm–2 4.8 [26]

28
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