Journal of Alloys and Compounds 925 (2022) 166748

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Journal of Alloys and Compounds

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

Innovative electrolytic cell of sulfur-doped MnO2 nanorods: Synergistic

hydrogen production and formaldehyde degradation at an ultra-low ]]
]]]]]]
]]

electric energy consumption

Wansheng Ruan, Shaoqian Shi, Qiuheng Wang, Xinyu Zhang, Weiyi Hao, Chen Yuan, Ben Ma,
⁎
Gangya Cheng, Fei Teng
Jiangsu Engineering and Technology Research Centre of Environmental Cleaning Materials (ECM), Jiangsu Collaborative Innovation Centre of Atmospheric
Environment and Equipment Technology (CICAEET), Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control (AEMPC), School of
Environmental Science and Engineering, Nanjing University of Information Science & Technology, 219 Ningliu Road, Nanjing 210044, China

a r t i cl e i nfo a bstr ac t

Article history: Electrocatalytic hydrogen production by water splitting is highly energy-intensive due to poor electro-
Received 23 May 2022 catalysts and sluggish four-electron oxygen evolution reaction (OER) kinetics. Herein, MnO2 and sulfur-
Received in revised form 4 August 2022 doped MnO2 (S-MnO2) are prepared by a simple hydrothermal method. The results show that S-MnO2
Accepted 10 August 2022
exhibits a higher OER activity than MnO2 because the sulfur doping gives rise to more Mn3+ active sites,
Available online 12 August 2022
oxygen vacancies (VO) and electrochemically active surface areas. Density functional theory (DFT) calcu-
lation further confirms that the abundant VO leads to a higher surface energy of S-MnO2, which is conducive
Keywords:
Electrocatalytic hydrogen production to the adsorptions of H2O and OH- on Mn3+ sites. Moreover, formaldehyde oxidation reaction (FOR) is
Formaldehyde degradation employed to substitute for sluggish OER to improve hydrogen evolution reaction (HER). Compared to OER-
Energy-efficient based electrolyzer (3.354 V), the cell voltage of FOR-based electrolyzer (2.778 V) at 100 mA cm−2 has de-
Synergistic creased by 17.17 %, and the Faradic efficiency of hydrogen production increases from 89.6 % to 98.6 %. The
Sulfur-doped MnO2 results indicates that to produce the same amount of hydrogen, 17.17 % of electric energy can be econo-
mized. Thus the cost of hydrogen production decreases greatly. The HER efficiency is greatly improved
because FOR has faster kinetics than OER. Meanwhile, after running for 2 h at 1.75 V, 52 % of formaldehyde
has been degraded. The results demonstrate that the innovative electrolyzer can not only greatly improve
the HER efficiency, but also efficiently degrade formaldehyde pollutants.
© 2022 Elsevier B.V. All rights reserved.

1. Introduction Moreover, this hydrogen production technology is highly energy-

intensive (1.8–2.0 V vs. RHE). Thus, it is still a big challenge to de-
In recent years, the development of clean energy has attracted velop an effective strategy to overcome the shortcomings above.
extensive attention. On the one hand, traditional fossil fuels as non- On the one hand, efficient electrocatalysts have an great influ-
renewable resources are consumed in vast amounts and are be- ence on water splitting. Usually, noble metal oxides such as RuO2
coming nearly exhausted [1]. On the other hand, a large number of and IrO2 are the most efficient OER electrocatalysts, however, the
harmful environmental pollutants are inevitably released during the high price and scarce reserves limit their wide applications.
use process of fossil fuels [2]. Hence, it is urgent to develop an ef- Therefore, it is desirable to develop efficient non-noble metals
ficient, sustainable green energy. Hydrogen with a high energy electrocatalysts. Among various transition metal oxides, manganese
density, as a clean energy, is considered as a good substitute for fossil oxides have attracted a particular attention to researchers, because
fuels [3]. Among various hydrogen production technologies, elec- of the low cost, environmental compatibility, variable valence and
trocatalytic water splitting is a highly attractive technology [4]. good thermal catalytic activity [7,8]. Typically, MnO2 shows an ex-
However, the overall efficiency of water splitting is severely affected cellent catalytic oxidation activity for volatile organic compounds
by the sluggish anodic oxygen evolution reaction (OER) [5,6]. (VOCs) [9]. However, MnO2 usually exhibits a poor OER activity due
to the limited number of exposed active sites. Generally, the doping
of atoms or ions is adopted to overcome this fault, for example, Kang
⁎
Corresponding author. et al. [10] reported that the doping of Au has significantly improved
E-mail address: [email protected] (F. Teng).

https://doi.org/10.1016/j.jallcom.2022.166748
0925-8388/© 2022 Elsevier B.V. All rights reserved.
W. Ruan, S. Shi, Q. Wang et al. Journal of Alloys and Compounds 925 (2022) 166748

Fig. 1. (a,b) X-ray diffraction (XRD) patterns; (c) Fourier-transform infrared spectra (FTIR); (d) Electron paramagnetic resonance (EPR) spectra.

the electronic structure and electronic conductivity of MnO2. conducive to the oxidation reaction. Moreover, an FOR-based elec-
Nevertheless, Au is expensive and the doping method is compli- trolyzer was assembled using S-MnO2 as both anode and cathode.
cated, which limit the wide applications. Besides, Kuang et al. [11] Compared to conventional electrolyzer, the FOR-based electrolyzer
have reported that the doping of sulfur optimized the active center exhibits a lower cell voltage and a higher Faradic efficiency.
of CoO electrocatalyst, thus showing an improved OER activity. In- Meanwhile, 52 % of formaldehyde was degraded after running for 2 h
spired by these results, we could expect that the OER activity of at 1.75 V. The results demonstrated that the innovative electrolyzer
MnO2 may also be improved through S doping. can not only greatly improve the hydrogen production efficiency, but
On the other hand, the substitution of easy-oxidized molecules also effectively degrade formaldehyde. From the viewpoint of energy
for sluggish OER is another effective strategy, including hydrazine and environment, this innovative electrolyzer is promising to be
[12], methanol [13], urea [14], ethanol [15] and formaldehyde [16,17], used for hydrogen production and wastewater clean simultaneously.
etc. Among them, the electrolytic oxidation of formaldehyde has
attracted the attention of researchers’. Since formaldehyde is an 2. Experimental section
easy-oxidized molecule [18], anodic formaldehyde oxidation reac-
tion (FOR) is expected to has a faster reaction kinetics than OER, 2.1. Materials
which may favor electron transfer. Moreover, formaldehyde as a
typical carcinogen could cause serious physiological diseases to Carbon cloth (CC) was purchased from Changsha Lyrun Material
human being, such as sensory stimulation, decreased immunity, Co., Ltd. The CC was washed ultrasonically in 3 M HCl aqueous so-
neurasthenia, gastrointestinal diseases and leukemia [19]. Therefore, lution for 15 min, then washed with water and ethanol 2–3 times,
it is imperative to purify formaldehyde wastewater. On base of the respectively. Finally, CC was dried at 30 °C for 24 h. All the other
analyses above, this work is tried to enhance hydrogen production chemicals were purchased from Shanghai Chemical Company in
efficiency and purify formaldehyde wastewater at the same time. China.
In this work, MnO2 and S-doped MnO2 (S-MnO2) were prepared
by a simple hydrothermal method and their electrocatalytic perfor- 2.2. Preparation of MnO2 and S-MnO2
mances were investigated. The results showed that S-MnO2 ex-
hibited a higher OER activity than MnO2 because S doping gives rise MnO2. Typically, 0.3039 g of KMnO4 was first dissolved in 39.4 mL
to more Mn3+ active sites, oxygen vacancies (VO) and higher elec- of deionized water, and then 0.6 mL of HCl aqueous solution
trochemically active surface areas (ECSA). Meanwhile, density (37 wt %) was added to the solution above under stirring. The so-
functional theory (DFT) calculation further confirms that S-MnO2 lution above was transferred to a 50 mL autoclave and was heated at
has more negative adsorption energies for H2O and OH-, which is 140 °C for 12 h.

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W. Ruan, S. Shi, Q. Wang et al. Journal of Alloys and Compounds 925 (2022) 166748

Fig. 2. (a,b) Scanning electron microscope (SEM) images; (c) Nitrogen sorption isotherms and (d) Pore size distribution.

Table 1
Surface element ratios and BET areas of the samples. Mn3O4, Mn2O3 and MnS can be identified, indicating that the in-
a b c c troduction of S does not change the crystal structure of MnO2.
Sample Surface element ratio BET Pore Average pore
area (m2 volume diameter Moreover, Fig. 1b shows that compared with MnO2, the diffraction
Mn3+: d
O-1:O-2 −1
g ) (cm3 g−1) (nm) peak of S-MnO2 at 2θ = 37.6° shifts to the left about 0.2 degrees,
Mn4+
confirming that S has been doped into the crystal lattice of
MnO2 0.58:1 10.5:1 19 0.04 8.6 MnO2 [10].
S-MnO2 1.22:1 5.38:1 40.9 0.10 10
Fourier-transform infrared spectra (FTIR) are performed to in-
a
Surface element ratio, calculated by corresponding peak area from X-ray photo- vestigate the chemical structure of the samples (Fig. 1c). The peaks at
electron spectroscopy (XPS);
b 3440 cm−1 and 1630 cm−1 correspond to the stretching vibration and
calculated by Brunauer-Emmett-Teller (BET) method;
c
calculated by Barrett-Joyner-Halenda (BJH) methods and deformation vibration, respectively, which indicates the presence of
d
O-1: Lattice oxygen, O-2: Hydroxyl oxygen. hydroxyls [20]. The peaks at 531 cm−1 and 457 cm−1 are ascribed to
the Mn-O stretching vibration of MnO6 octahedron [21]. Compared
with MnO2, the peaks intensities at 531 cm−1 and 457 cm−1 of S-
S-MnO2. Typically, 50 mg of the as-obtained MnO2 above was MnO2 decrease obviously, suggesting that S-MnO2 has fewer Mn-O
dispersed into 30 mL of ethanol, 30 mg of thioacetamide was added bonds. Besides, electron paramagnetic resonance (EPR) spectroscopy
to the suspension above, and the suspension was stirred for 0.5 h. was performed to explore the defect property [22]. As displayed in
Finally, the suspension was transferred to a 50 mL autoclave and was Fig. 1d, the EPR signal at g = 2.003 can be assigned to oxygen vacancy
heated at 120 °C for 12 h. (VO) [23]. Compared to MnO2, the higher signal intensity of S-MnO2
The material characterization, electrochemistry test, determina- indicates that more VO are contained in S-MnO2.
tion of Faradaic efficiency and DFT calculation were placed in the Furthermore, scanning electron microscope (SEM) is done to
electronic supporting information (ESI). observe the particle morphology. As observed from Figs. 2a and 2b,
the MnO2 sample is composed of uniform nanorods, which are
3. Results and discussion 150–200 nm in diameter and 1–3 µm in length. S-MnO2 also shows
the similar morphology. Besides, Figs. 2c and 2d show the nitrogen
3.1. Characterization of the sample sorption isotherms and pore size distribution curves of both sam-
ples, respectively. It is obvious that the mesoporous MnO2 and S-
The X-ray powder polycrystalline diffractometer (XRD) is em- MnO2 form. The Brunauer-Emmett-Teller (BET) areas of MnO2 and S-
ployed to characterize phase compositions of MnO2 and S-MnO2 MnO2 are 19 and 40.9 m2 g−1, respectively; the pore volumes of
samples (Fig. 1a). For MnO2 sample, the diffraction peaks are well MnO2 and S-MnO2 are 0.04 and 0.10 cm−3 g−1, respectively; and the
indexed as the PDF#72–1982 [9], confirming the formation of average pore diameters of MnO2 and S-MnO2 are 8.6 and 10 nm,
tetragonal MnO2. For S-MnO2 sample, all the diffraction peaks are respectively (Table 1). It can be seen that the doping of S has im-
also indexed as the PDF#72–1982 [9], no diffraction peaks of proved the BET area and pore volume.

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W. Ruan, S. Shi, Q. Wang et al. Journal of Alloys and Compounds 925 (2022) 166748

Fig. 3. X-ray photoelectron spectroscopy (XPS): (a) Survey XPS; (b) O 1 s XPS; (c) Mn 2p XPS; (d) S 2p XPS.

X-ray photoelectron spectroscopy (XPS) was conducted to in- are 0.9 %, 20.2 % and 46.32 %, respectively; and the surface atom ratios
vestigate the surface compositions and chemical states of the sam- of S: Mn: O is 0.04: 1: 2.29.
ples. As shown in Fig. 3a, the survey XPS spectra confirm that Mn and
O are contained in MnO2 sample, while Mn, O and S are contained in 3.2. Effect of sulfur doping on water electrolysis
S-MnO2 sample. For O 1 s XPS spectra (Fig. 3b), three sub-bands can
be found for both samples, the sub-band at around 529.8 eV (O-1) The OER activities of MnO2 and S-MnO2 samples were measured
belongs to lattice oxygen (Mn-O-Mn), and the sub-band at around in a three-electrode system using 1 M KOH solution as the electro-
531.4 eV (O-2) belongs to the O of hydroxyl [24,25]. Moreover, the XPS lyte. Fig. 4a shows that compared with MnO2, S-MnO2 exhibits a
peaks of VO locate at 531.28 and 530.91 eV for MnO2 and S-MnO2, higher current density and a lower onset potential. At 10 mA cm−2,
respectively [26]. It is can be seen that the introduction of S increases the potential of S-MnO2 is only 1.68 V (vs. RHE), which is much
the concentration of VO, which is consistent to the EPR results. Fig. 3c smaller than that of MnO2 (1.76 V vs. RHE). Fig. 4b presents the
presents the Mn 2p XPS spectra of MnO2 and S-MnO2 samples. For current densities at different overpotentials. At 500, 550 and
MnO2, the Mn 2p3/2 peak can be deconvoluted into Mn3+ and Mn4+ 600 mV, the current densities of S-MnO2 are 30.8, 80.2 and
sub-bands at 642.43 and 643.31 eV, respectively [27], and the Mn 2p1/ 158.3 mA cm−2, respectively, which are significantly higher than that
3+
2 peak can be also deconvoluted into Mn and Mn4+ sub-bands at of MnO2 (6.4, 13.6, and 27.5 mA cm−2), respectively. Typically at
653.83 and 654.71 eV, respectively. Meanwhile, for S-MnO2, the Mn 600 mV, the current density of S-MnO2 is 4.75 times higher than that
2p3/2 peak can be deconvoluted into Mn3+ and Mn4+ sub-bands at of MnO2. It is obvious that S-MnO2 has a higher OER activity than
642.09 and 643.73 eV, respectively [28], and the Mn 2p1/2 peak can be MnO2. Moreover, Fig. 4c shows that the Tafel slope of S-MnO2 is
also deconvoluted into Mn3+ and Mn4+ sub-bands at 653.49 and 92.86 mV/dec, which is much lower than that of MnO2 (173.06 mV/
655.13 eV, respectively. Furthermore, the surface atoms ratios were dec), confirming a fast OER kinetics of S-MnO2. Furthermore, Table
calculated by corresponding peak areas (Table 1). The atomic ratios of S2 (seeing ESI) lists the OER performance comparison. It can be seen
Mn3+: Mn4+ are 0.58:1 and 1.22:1 for MnO2 and S-MnO2, respectively. that the Tafel slope of S-MnO2 is lower than most of the reported
While the atomic ratios of O-1: O-2 are 10.5: 1 and 5.38: 1 for MnO2 results.
and S-MnO2, respectively. It can be seen that compared with MnO2, S- Usually, the active site number of electrocatalyst is directly pro-
MnO2 contains more Mn3+ and hydroxyl oxygen, which could be at- portional to the electrochemically active surface area (ECSA) [33].
tributed to the breakage of Mn-O bond and the formation of VO [29]. The ECSA is determined by the electrochemical double-layer capa-
This result is consistent to the FTIR and EPR results. Furthermore, citance (Cdl) [34,35], which can be estimated by cyclic voltammetry
Fig. 3d displays the S 2p XPS spectroscopy for S-MnO2, the fitted (CV) (Fig. S1, seeing ESI). As shown in Fig. 4d, the Cdl value of S-MnO2
peaks at about 168 and 168.6 eV correspond to S4+ and S6+, respec- (84.2 mF cm−2) is approximately 1.5 times as high as that of MnO2
tively [30]. In addition, the surface elements contents of the samples (56.09 mF cm−2), indicating that S-MnO2 has more electrochemically
were determined by XPS through integral peak areas [31,32]. As active sites. Fig. S2 (seeing ESI) displays the EIS Nyquist plot, and the
shown in Table S1 (seeing ESI), the atom percentages of S, Mn and O inset shows the simulated equivalent electric circuit (EEC). The EEC

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W. Ruan, S. Shi, Q. Wang et al. Journal of Alloys and Compounds 925 (2022) 166748

Fig. 4. Oxygen evolution reaction (OER) performances: (a) Linear sweep voltammetry (LSV) curves; (b) Current densities at different overpotentials; (c) Tafel plots; (d) Current
density difference (ΔJ =Ja-Jc) against scan rate at a potential of 1.15 V (vs. RHE); (e) Z′ vs. the reciprocal of the square root of frequency (ω−0.5) in the intermediate frequency range;
(f) cycle stability for CV scanning.

is composed of electrolyte solution resistance (RS), constant phase reciprocal of the square root of frequency (ω−0.5) [38–40]. It can be
element of an electric double-layer capacitor (CPE), charge transfer seen that the σ value of S-MnO2 is about 3.8 times smaller than that
resistance (Rct), and Warburg resistance (W0). Through calculation, of MnO2, indicating that S-MnO2 has an ultrafast ion diffusion ki-
the Rs values of MnO2 and S-MnO2 are 2.91 and 2.68 Ω, respectively; netics than MnO2 [41–43]. In addition, Fig. 4f shows the OER po-
and the Rct values are 2.9 and 0.3 Ω for MnO2 and S-MnO2, respec- larization curves of the samples for the 1st and 1000 cycles. After
tively. Compared with MnO2, the smaller Rct of S-MnO2 indicates a 1000 cycles, the polarization curve is almost unchanged. Fig. S3
higher electronic conductivity [36,37]. Moreover, Fig. 4e presents the (seeing ESI) further shows the current density curves at a constant
diffusion resistances (σ) of MnO2 and S-MnO2, the σ values are ob- potential while running for 20 h. The results above indicate both
tained from the slopes of the real part of impedance (Z′) versus the MnO2 and S-MnO2 have a good stability.

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W. Ruan, S. Shi, Q. Wang et al. Journal of Alloys and Compounds 925 (2022) 166748

Fig. 5. (a,c) Crystal structure and (b,d) (100) facet structure: (a,b) MnO2; (c,d) S-MnO2.

Table 2 octahedrons, with 2 × 2 tunnel structure and the tunnel size is ~4.6 Å
Surface energy (Esurf) and adsorption energy (Eads) of MnO2 (100) and S-MnO2 (100) [9]. Meanwhile, Fig. 5b shows the (100) facet structure of MnO2.
facets. Besides, we have optimized and simulated the crystal structure
Material Esurf a
H2O- b
OH-- c
HCHO- (Fig. 5c) and (100) facet structure (Fig. 5d) of S-MnO2. It is seen that
(J/m2) Eads (eV) Eads (eV) Eads (eV) sulfur atom preferentially occupy the interstitial site of MnO2. Kang
MnO2 (100) 0.11 -0.8 -1.6 3.6 et al. [10] have also reported the similar result. As shown in Table 2,
S-MnO2 (100) 0.14 -1.78 -2.16 2.4 the Esurf of (100) facet is 0.11 J/m2 and 0.14 J/m2 for MnO2 and S-
a
the Eads of H2O; MnO2, respectively. The higher Esurf indicates that S-MnO2 is more
b
the Eads of OH- and reactive than MnO2.
c
the Eads of HCHO Furthermore, Fig. 6(a,b) and 6(d,e) present the optimized ad-
sorption modes of OH- and H2O on (100) facets of MnO2 and S-MnO2,
3.3. Density functional theory (DFT) calculation respectively. As summarized in Table 2, the Eads values of H2O (H2O-
Eads) on MnO2 and S-MnO2 are −0.8 eV and −1.78 eV, respectively.
To further understand the effects of sulfur doping on electro- Meanwhile, the Eads values of OH- (OH--Eads) on MnO2 and S-MnO2
catalytic activity, the DFT calculation was carried out for MnO2 and are −1.6 eV and −2.16 eV, respectively. Compared to on MnO2, the
S-MnO2. Rong et al. [44] have demonstrated that the surface of MnO2 more negative H2O-Eads and OH--Eads suggest that the H2O and OH-
nanorods mainly consists of the (100) facet, thus the surface energy adsorptions on S-MnO2 are more favorable thermodynamically,
(Esurf) and adsorption energy (Eads) of (100) surface were calculated. which would benefit the oxidation reaction.
Fig. 5a shows the crystal structure of MnO2, which consists of double Based on the above results, a plausible OER mechanism over S-
chains and angle-shared double chains of edge-shared MnO6 MnO2 is proposed (Fig. 7). The OER process is carried out through

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W. Ruan, S. Shi, Q. Wang et al. Journal of Alloys and Compounds 925 (2022) 166748

Fig. 6. Optimized adsorption modes on MnO2-100 facet and S-MnO2-100 facet: (a,e) OH-; (b,f) H2O; (c,g) HCHO.

four single-electron transfer steps, and five elementary steps are various manganese oxides including Mn3+, Mn4+ and mixed-valence
shown in Eqs. (1–5) as follows [45], in which * denotes the active manganese. They have proved the key role of Mn3+ in water oxidation
site. It seems that *OH, *O and *OOH may be the active intermediates reaction. In addition, Jia et al. [49] have confirmed that Co-doped
that participate in the charge transfer process. MnO2 with abundant surface VO has a greatly improved OER activity.
Similarly, the DFT calculation further confirmed that H2O-Eads and
* +OH *OH + e (1)
OH--Eads on S-MnO2 with VO are more negative than those on MnO2
*OH + OH H2 O + *O + e (2) without VO, suggesting that the H2O and OH- adsorptions on S-MnO2
with VO are more favorable thermodynamically, which would benefit
*O + OH *OOH + e (3) the oxidation reaction. Thus, we could hold that compared with the
MnO2 sample, the higher OER activity of the S-MnO2 sample is attri-
*OOH + OH *O2 + H2 O + e (4) bute to the synergistic effect of VO and Mn3+.
Furthermore, Fig. S4 (seeing ESI) shows the optimized adsorption
*O2 O2 + e (5)
modes for H* on the (100) surfaces of MnO2 without VO and S-MnO2
3+
According to the XPS and EPR results, S-MnO2 has more Mn and with VO, respectively; and Fig. S5 (seeing ESI) shows the Gibbs ad-
VO than MnO2. Herein, Mn3+ is likely to be the active center. The un- sorption free energies for H* (ΔGH*) on them. It is obvious that S-
stable Mn3+ in MnO6 octahedron is easy to adsorb OH- to form *OOH MnO2 with VO has a more favorable ΔGH* than MnO2 without VO,
(Eq. 3) [46], which dynamically accelerates the release of oxygen [47]. further demonstrating that the S-MnO2 sample has a higher HER
In this aspect, Smith et al. [48] investigated the catalytic activities of activity than the MnO2 sample.

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W. Ruan, S. Shi, Q. Wang et al. Journal of Alloys and Compounds 925 (2022) 166748

Fig. 7. A plausible OER mechanism on S-MnO2 in alkaline medium.

Fig. 8. Effects of HCHO concentration on anodic oxidation reaction: (a,d) LSV curves; (b,e) Tafel plots; (c,f) Current densities at different overpotentials.

3.4. Boosted hydrogen production efficiency by formaldehyde curves of MnO2. It is seen that the anode current density increases
significantly after adding formaldehyde. Fig. 8b displays the corre-
Formaldehyde (HCHO) was added to the KOH solution to further sponding Tafel plots. When the HCHO concentration added is 0.5 and
improve the electrocatalytic performance. Fig. 8a presents the LSV 1 mg/L, the Tafel slopes are 156.79 and 142.82 mV/dec, respectively,

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W. Ruan, S. Shi, Q. Wang et al. Journal of Alloys and Compounds 925 (2022) 166748

Fig. 9. (a) Optical image for overall electrolytic cell using 1 M KOH/1 mg/L HCHO as electrolyte; (b) Polarization curves of formaldehyde oxidation reaction (FOR)-based elec-
trolyzer and OER-based electrolyzer at a scanning rate of 5 mV s−1; (c) Cell voltage of S-MnO2 at different current densities. Notes: for OER- and FOR- based electrolyzers, 1 M KOH
and 1 M KOH/1 mg/L HCHO solutions are used as the electrolytes, respectively; while their cathode and anode are both with S-MnO2.

Table 3 oxidation reaction, and S-MnO2 has an obviously higher FOR activity
The performance parameters of the electrolyzers using S-MnO2 as both anode and than MnO2.
cathode at 100 mA cm−2. Furthermore, DFT calculation was done to investigate the HCHO
Entry 1 M KOH 1 M KOH + 1 mg/L HCHO adsorptions on S-MnO2 and MnO2. Figs. 6c and 6f show the opti-
a
AOR (V) 1.366 0.968
mized adsorption structure modes of HCHO on them. It is seen that
b
HER (V) -1.988 -1.81 HCHO molecules preferentially adsorb on Mn sites. As shown in
Cell voltage (V) 3.354 2.778 Table 2, the adsorption energy of HCHO on S-MnO2 (2.4 eV) is
Decrease of cell voltage (V) / 0.576c smaller than that on MnO2 (3.6 eV), suggesting that the HCHO ad-
Decrease ratio of cell voltage ( %) / 17.17c
sorption on S-MnO2 is easier than on MnO2. Therefore, S-MnO2
a
anodic oxidation reaction; shows a higher FOR activity than MnO2.
b
hydrogen evolution reaction and On base of the results above, a FOR-based electrolyzer was de-
c
compared with that only using 1 M KOH solution as electrolyte.
signed with 1 M KOH/1 mg/L HCHO solutions as the electrolyte and
using S-MnO2 as both cathode and anode. It is seen from Fig. 9a and
which are significantly smaller than that in KOH solution
Video I (seeing Supplementary video) that hydrogen continuously
(173.06 mV/dec). Such a low Tafel slope indicates a faster electro-
bubbles out on the cathodes. Besides, Fig. 9b displays the polariza-
catalytic reaction kinetics of formaldehyde oxidation reaction (FOR),
tion curves of OER-based electrolyzer and FOR-based electrolyzer,
compared to OER. At 2 mg/L HCHO added, however, the Tafel slope
and Fig. 9c and Table (3, S3 and S4, seeing ESI) summarize the per-
(177.1 mV/dec) slightly increases. We could assume that during the
formance parameters of both electrolyzers. For the OER-based
FOR process, some intermediates species (e.g., formate, methanol,
electrolyzer, the required anodic oxidation potentials at 20, 50 and
etc.) may be generated and adsorb on the active sites. It is reasonable
100 mA cm−2 are 1.024, 1.205 and 1.366 V, respectively; while for
that a higher concentration of HCHO would result in more inter-
FOR-based electrolyzer, the required anodic oxidation potentials are
mediates species. As a result, the competitive adsorption of inter-
only 0.821, 0.916 and 0.968 V, respectively. Meanwhile, for the
mediates species would impede the adsorption and oxidation of
cathodic reduction reaction of OER-based electrolyzer, the required
HCHO [16]. As a result, the FOR kinetics becomes slower at 2 mg/L
potential is −1.474, −1.865 and −1.988 V at 20, 50 and 100 mA cm−2,
HCHO. Moreover, Fig. 8c shows the different current densities at the
respectively; while for FOR-based electrolyzer, the required poten-
same potential. It can be clearly seen that after adding HCHO, the
tials are only −1.451, −1.739 and − 1.81 V, respectively. Thus, to reach
anodic current density increases. In addition, Fig. 8d shows the LSV
20, 50 and 100 mA cm−2, the required cell voltages of OER-based
curves of S-MnO2. The addition of HCHO has also improved current
electrolyzer are 2.498, 3.07 and 3.354 V, respectively; but the cell
density significantly. Especially, while adding 1 mg/L HCHO, the Tafel
voltage of FOR-based electrolyzer are 2.272, 2.655 and 2.778 V, re-
slope (Fig. 8e) is only 67.5 mV/dec, confirming an excellent oxidation
spectively. Compared with OER-based electrolyzer, the required cell
reaction kinetics. At 1 mg/L HCHO added, S-MnO2 shows the best
voltages of FOR-based electrolyzer have decreased by 0.226, 0.415
FOR performance (Fig. 8f). Specifically, At 1.85 V (vs. RHE), the OER
and 0.576 V at 20, 50 and 100 mA cm−2, respectively, namely, the cell
current density in 1 M KOH solution is 196.6 mA cm−2, while the
voltages have decreased by 9.05 %, 13.52 % and 17.17 %, respectively.
current density in 1 M KOH + 1 mg/L HCHO reaches 328.5 mA cm−2.
The results confirm that to produce the same amount of hydrogen,
Summarily, the addition of HCHO can greatly improve the anodic

Fig. 10. (a) Theoretical (black line) and experimental data of hydrogen volume (VH2) over S-MnO2 cathode at 20 mA; (b) Calculated Faradaic efficiency (FE); (c) Removal ratio of
formaldehyde after 2 h at 1.75 V.

9
W. Ruan, S. Shi, Q. Wang et al. Journal of Alloys and Compounds 925 (2022) 166748

about 9.05 %−17.17 % of electric energy can be economized, thus Acknowledgments

hydrogen production cost can be decreased greatly.
In order to investigate the influence of FOR on HER efficiency, H2 This work is financially supported by Royal Society International
evolution amounts over the S-MnO2 cathode were examined in 1 M Exchanges Program (Ref: IES\R1\211133), Longshan Scholar Project
KOH and 1 M KOH/1 mg/L HCHO solutions, respectively. The mon- (2020t2411), National Natural Science Foundation of China
itoring setup is shown in Fig. S6 (seeing ESI) and Video (II) (seeing (22177543) and Postgraduate Research & Practice Innovation
Supplementary videos). Fig. 10a shows the correlation of the volume Program of Jiangsu Province (SJCX22_0365).
of hydrogen produced with reaction time at a constant cathodic
current of 20 mA. Fig. 10b presents the Faradic efficiency on base of Appendix A. Supporting information
HER. The Faradaic efficiencies are 89.6 % and 98.6 % in 1 M KOH, and
1 M KOH/1 mg/L HCHO electrolytes, respectively. This result con- Supplementary data associated with this article can be found in
firms that the FOR-based electrolyzer has a higher conversion effi- the online version at doi:10.1016/j.jallcom.2022.166748.
ciency from electric energy to chemical energy than the OER-based
electrolyzer. References
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