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Article

Ultrafast Synthesis of Mo2C-Based Catalyst by Joule Heating towards Electrocatalytic Hydrogen Evolution Reaction

by
Hefeng Zhang
,
Shengliang Qi
,
Kaixin Zhu
,
Haidong Wang
,
Guanghui Zhang
,
Weiguang Ma
* and
Xu Zong
*
Marine Engineering College, Dalian Maritime University, Linghai Road 1, Dalian 116026, China
*
Authors to whom correspondence should be addressed.
Symmetry 2023, 15(4), 801; https://doi.org/10.3390/sym15040801
Submission received: 8 March 2023 / Revised: 22 March 2023 / Accepted: 24 March 2023 / Published: 25 March 2023
(This article belongs to the Section Chemistry: Symmetry/Asymmetry)
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Abstract

:
Developing earth-abundant electrocatalysts useful for hydrogen evolution reactions (HER) is critical for electrocatalytic water splitting driven by renewable energy. Molybdenum carbide (Mo2C) with the crystal structure of hexagonal symmetry has been identified to be an excellent HER catalyst due to its platinum-like electronic structure while the synthesis of Mo2C is generally time consuming and energy intensive. Herein, we demonstrated the ultrafast synthesis of a Mo2C-based electrocatalyst with Joule heating at 1473 K for only 6 s. Benefitting from several advantages including efficient catalytic kinetics, enhanced charge transport kinetics and high intrinsic activity, the as-prepared catalyst exhibited drastically enhanced HER performance compared with commercial Mo2C. It showed an overpotential of 288 mV for achieving a current density of −50 mA cm−2 and good stability, which highlighted the feasibility of the Joule heating method towards preparing efficient electrocatalysts.

1. Introduction

The production of hydrogen (H2) through electrocatalytic water splitting is a promising approach to convert renewable energy into storable chemical energy [1,2,3,4,5,6]. The hydrogen evolution reaction (HER) is critical in water electrolysis processes. However, because of the sluggish reaction kinetics of HER, a large overpotential must be overcome [7,8]. As a result, identifying efficient electrocatalysts to reduce the HER energy barrier is highly desirable [9,10]. Although noble metals such as Pt have been considered the benchmark catalysts for HER [11], their high costs and scarcity severely limit their large-scale applications [12,13]. Therefore, developing a high-performance electrocatalyst based on noble-metal-free materials is essential.
In the past few decades, a range of earth-abundant materials, including metal nitride [14,15], sulphide [16,17], phosphide [18,19], carbide [20,21], and alloys [22,23], have been identified as excellent catalysts for the HER process. Among all these materials, molybdenum carbide (Mo2C) with hexagonal crystal symmetry has emerged as a strong contender due to its platinum-like electronic structure [24,25,26]. For example, Ma et al. demonstrated that Mo2C nanoparticles coated with 1–3 graphene layers exhibited an excellent HER performance with an overpotential of 78 mV for achieving a current density of 10 mA cm−2 [27]. Cheng et al. fabricated an electrocatalyst with a ribbon-like nanostructure by embedding Mo2C in nitrogen-doped carbon nanomesh [28]. This catalyst displayed superior HER activity comparable to commercial Pt/C in 0.5 M H2SO4. Up to now, several methods have been developed for the synthesis of Mo2C catalyst, such as carbonization of metal complexes [29], chemical vapor deposition [30], and pyrolysis of metal precursors [31]. Different synthesis approaches affect the surface structure and therefore the HER performance of Mo2C [24,32]. However, although these methods can successfully prepare Mo2C, annealing at high temperatures and for long durations is inevitable because of the slow reaction kinetics between solid–solid interfaces [33,34,35].
Recently, Joule heating has emerged as an attractive method for synthesizing a variety of materials, such as graphene [36,37], high-entropy alloy nanoparticles [38,39], and single-atom catalysts [40,41]. In the process of Joule heating, a current pulse will flow through the precursor, thus allowing for the rapid heating of the precursor to the desired reaction temperature, followed by rapid cooling to room temperature [42], which demonstrates the possibility of using Joule heating to synthesize Mo2C.
In this work, we reported the successful synthesis of a Mo2C-based electrocatalyst using an ultrafast Joule heating method. The synthesis was time-saving, which can be completed in just 6 s at 1473 K. The as-prepared Mo2C-based electrocatalyst exhibited an overpotential of 288 mV to yield a current density of −50 mA cm−2 for HER. Moreover, after 1000 cycles of cyclic voltammetry, the current density showed no apparent degradation. The good performance of the as-prepared catalyst was mainly attributed to the efficient catalytic kinetics, high intrinsic activity and reduced charge transfer resistance between the catalyst and electrolyte interface.

2. Materials and Methods

2.1. Reagents

(NH4)6Mo7O24·4H2O was bought from Aladdin Reagent Ltd. Carbon paper and carbon black were supplied by Gaossunion. Nafion (5 wt%) was purchased from Alfa Aesar. Ethanol was provided by Tianjin Damao Chemical Reagent Co., Ltd. All the chemicals in this study were purchased commercially and used without further purification. Deionized (DI) water from a Milli-Q purification system (resistivity > 18 MΩ cm) was used to prepare solutions.

2.2. Preparation of the Mo2C-Based Electrocatalyst

The Mo2C-based electrocatalyst was synthesized by ultrafast Joule heating according to the reported method with some modifications [40]. (NH4)6Mo7O24·4H2O and carbon black (molar ratio Mo:C = 1:10) were mixed and ground by using a mortar and pestle. The mixture (20 mg) was loaded into a conductive carbon paper. The conductive carbon paper was then put onto a reaction platform. The reaction platform was placed into the chamber and connected to the Joule heating instrument (Eshock Co., Ltd. Changchun, China). When the system was evacuated to a pressure of 150 Pa, the reaction was carried out. The temperature quickly soared to 1473 K with a heating rate of ca. 5000 K s−1. After being heated for 6 s at 1473 K, the temperature rapidly dropped to room temperature at a rate of ca. 1000 K s−1.

2.3. Material Characterizations

X-ray diffraction (XRD) patterns were obtained on a Rigaku D/Max-2500/PC powder diffractometer equipped with Cu Kα radiation. The morphology was investigated by scanning electron microscopy (SEM, Quanta 200 FEG). High-resolution transmission electron microscopy (HRTEM) was conducted by a JEM-2100F. X-ray photoelectron spectroscopy (XPS) was carried out on a Thermo ESCLAB 250Xi with a monochromatic Al Kα X-ray source. The obtained XPS spectra were analyzed by XPSPEAK software.

2.4. Electrode Preparation

The carbon paper was cut into squares with an area of 0.5 × 0.5 cm2, and then washed by ultrasonication in ethanol and DI water for 20 min, respectively. Next, 1 mg of Mo2C-based electrocatalyst was dispersed in a solution containing 50 μL DI water, 45 μL ethanol and 5 μL Nafion (5 wt%). The mixture was then sonicated for 20 min to form a catalyst ink. Afterwards, 35 μL of the ink was dropped onto the carbon paper and allowed to dry at room temperature.

2.5. Electrochemical Measurements

The electrochemical measurements were performed using a CHI 660E potentiostat in 0.5 M H2SO4. A three-electrode configuration was used with the drop-coated carbon paper electrode, a graphite plate and a saturated calomel electrode (SCE) as the working, counter and reference electrodes, respectively. Linear sweep voltammetry (LSV) curves were recorded at a scan rate of 10 mV s−1 without iR compensation. Cyclic voltammetry (CV) tests were conducted from −0.27 V to −0.53 V at a scan rate of 100 mV s−1. Electrochemical impedance spectroscopy (EIS) was carried out at −0.48 V using an amplitude of 5 mV and a frequency range of 0.05 Hz to 100 kHz. The measured potentials versus SCE were transferred to the reversible hydrogen electrode (RHE) scale employing the following equation: ERHE = ESCE + 0.2415 V + 0.059 × pH.

3. Results and Discussion

Figure 1a shows the schematic procedure for the ultrafast preparation of a Mo2C-based catalyst via the Joule heating method. A mixture of (NH4)6Mo7O24·4H2O and carbon black (CB) was heated at 1473 K for 6 s under a pressure of 150 Pa. During the Joule heating process, bright light radiation was released (Figure 1b) because of high temperature produced by the current pulse. As a result, the Mo precursors quickly reacted with the CB, thus forming the Mo2C-based catalysts.
The crystal structure of the catalyst was analyzed by XRD. As shown in Figure 2a, the XRD pattern of the as-prepared sample displayed a set of diffraction peaks. The broad diffraction peak located at 21° was assigned to CB according to the literature [43]. Other distinctive diffraction peaks can be well indexed to Mo2C and Mo, respectively. Therefore, a composite catalyst of Mo2C and Mo anchored on CB was obtained (denoted as Mo2C-Mo/CB). The morphology of the Mo2C-Mo/CB electrocatalyst was investigated by SEM. Figure 2b,c demonstrated that the sample exhibited a nanoparticle morphology with no obvious agglomeration.
The structures of Mo2C-Mo/CB were further characterized by HRTEM. Figure 3a showed that the Mo2C-Mo nanoparticles were evenly and intimately anchored on the CB surface. Figure 3b exhibited that the average particle size of the Mo2C-Mo nanoparticle was 12 nm. The small particle size indicated rapid nucleation kinetics because of the high temperature provided instantaneously by the Joule heating method [44,45,46]. As shown in Figure 3c, lattice fringes with an interspace of 0.22 nm and 0.23 nm were observed in the HRTEM image, corresponding to the (110) lattice plane of metallic Mo and the (101) lattice plane of Mo2C, respectively. Moreover, energy-dispersive spectroscopy (EDS) mapping images revealed the distribution of elemental Mo and C. Figure 3d showed that the Mo and C elements were uniformly distributed over the catalyst particles.
XPS was used to investigate the chemical compositions of the Mo2C-Mo/CB. As shown in Figure 4a, there were four chemical states for the Mo, including Mo6+, Mo4+, Mo2+ and Mo0. Peaks at 228.6 and 231.8 eV can be assigned to the 3d5/2 and 3d3/2 of Mo0, respectively [47,48]. Peaks located at 228.8 and 232.2 eV can be assigned to the 3d5/2 and 3d3/2 of Mo2+, respectively [47,48]. Other peaks can be attributed to Mo6+ and Mo4+, respectively [48,49]. As for C, peaks at 284.2 eV (C 1s) and 284.8 eV (C 1s) can be assigned to carbon species of C-Mo and C-C, respectively (Figure 4b) [50,51]. Other peaks can be indexed to carbon species of C-O and O=C-O, respectively [50,51]. According to previous studies [48,52], the presence of higher-valence Mo and C species such as Mo6+, Mo4+, C-O and O=C-O was ascribed to superficial oxidation upon exposure to air. Therefore, these results indicated that the Mo2C-Mo/CB catalyst was successfully synthesized via the present Joule heating method.
The HER performances of the Mo2C-Mo/CB electrocatalyst were evaluated in 0.5 M H2SO4 with a three-electrode system. For comparison, the HER performances of bare carbon paper and commercial Mo2C were also investigated. As shown in Figure 5a, the bare carbon paper demonstrated a negligible cathodic current density. Meanwhile, commercial Mo2C showed an overpotential of 300 mV to achieve a current density of −8 mA cm−2. In contrast, the Mo2C-Mo/CB exhibited significantly enhanced HER activity, requiring an overpotential of 180 mV to yield a current density of −8 mA cm−2. Additionally, an impressive current density of −50 mA∙cm−2 was achieved for the Mo2C-Mo/CB electrocatalyst at an overpotential of 288 mV. The Tafel slope can be calculated from the linear sweep voltammetry curve, which reflects the reaction kinetics [53,54]. As shown in Figure 5b, Mo2C-Mo/CB displayed a smaller Tafel slope (125 mV dec−1) than that of commercial Mo2C (458 mV dec−1), demonstrating more efficient HER catalytic kinetics of Mo2C-Mo/CB. Moreover, the Mo2C-Mo/CB exhibited good stability for HER. After 1000 cycles of cyclic voltammetry, no obvious decrease in current density was observed (Figure 5c). The good stability of Mo2C-Mo/CB was ascribed to the immobilization of the Mo2C-Mo nanoparticle on CB, which can avoid the detachment of the Mo2C-Mo nanoparticle in the HER process. Furthermore, The EIS analysis was employed to investigate the change in charge transfer resistance between the catalyst and electrolyte interface [55,56]. As shown in Figure 5d, the charge transfer resistance of Mo2C-Mo/CB was lower than that of commercial Mo2C, which indicated that the Mo2C-Mo/CB could act as a facilitator to drastically enhance charge transport kinetics. The lower charge transfer resistance may be attributed to the formation of an efficient charge transfer channel in the Mo2C-Mo/CB electrocatalyst.
In addition, the double-layer capacitance (Cdl) of the electrocatalyst was measured. The electrochemically active surface area (ECSA) is usually related to Cdl [57,58]. Figure 6a showed that the capacitance of Mo2C-Mo/CB (49.7 mF cm−2) was higher than that of commercial Mo2C (9.5 mF cm−2), which indicated that Mo2C-Mo/CB possessed increased ECSA and catalytic active sites for HER. This may be because of the smaller Mo2C-Mo particle size in Mo2C-Mo/CB. Furthermore, Figure 6b presents the normalization of the geometric current density with active site concentration at an overpotential of 300 mV. Because of the unknown capacitive behavior (Cs) of the Mo2C, active site activity*Cs (ASA*Cs) was employed to compare the intrinsic activity [59,60]. The ASA*Cs of Mo2C-Mo/CB was 1.18 mA cm−2, which was larger than that of commercial Mo2C (0.83 mA cm−2). Therefore, it is reasonable to demonstrate that the good performance of Mo2C-Mo/CB catalyst is attributed to efficient catalytic kinetics, enhanced charge transport kinetics and high intrinsic activity.

4. Conclusions

In conclusion, we employed an ultrafast Joule heating method to prepare a Mo2C-Mo/CB electrocatalyst for HER. The reaction was conducted at 1473 K for only 6 s. The Mo2C-Mo/CB electrocatalyst showed an overpotential of 288 mV to achieve a current density of −50 mA cm−2. Furthermore, after 1000 cycles of cyclic voltammetry, no obvious decrease in current density was observed. The good activity and durability of the Mo2C-Mo/CB electrocatalyst was due to the favourable catalytic kinetics, decreased charge transport resistance and high intrinsic activity. The earth-abundant nature and good electrochemical performance of Mo2C-Mo/CB will enable it to be a promising candidate for future electrocatalytic hydrogen evolution driven by renewable energy.

Author Contributions

Conceptualization, X.Z. and W.M.; data curation, H.Z. and S.Q.; investigation, H.Z. and K.Z.; methodology, G.Z.; resources, H.W.; validation, S.Q. and K.Z.; supervision, X.Z. and W.M.; writing—original draft preparation, H.Z. and X.Z.; writing—review and editing, X.Z. and W.M. All authors have read and agreed to the published version of the manuscript.

Funding

This work was Funded by China Postdoctoral Science Foundation (grant number 2021M700651), the Fundamental Research Funds for the Central Universities (grant number 3132022216 and 3132022217).

Data Availability Statement

The data presented in this study are available on request from the corresponding authors.

Conflicts of Interest

The authors declare no conflict of interest.

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Symmetry 15 00801 g001 550
Figure 1. (a) The schematic illustration of the synthesis of the Mo2C-based catalyst with Joule heating. (b) The picture of the Joule heating system during synthesis.
Figure 1. (a) The schematic illustration of the synthesis of the Mo2C-based catalyst with Joule heating. (b) The picture of the Joule heating system during synthesis.
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Figure 2. (a) XRD patterns of Mo2C-Mo/CB and carbon black; (b) and (c) SEM images of Mo2C-Mo/CB with different scale bars.
Figure 2. (a) XRD patterns of Mo2C-Mo/CB and carbon black; (b) and (c) SEM images of Mo2C-Mo/CB with different scale bars.
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Figure 3. (a) TEM image of the Mo2C-Mo/CB catalyst. (b) The statistics of Mo2C-Mo/CB particle size distribution. (c) HRTEM image of the interface between Mo2C (101) and Mo (110) in Mo2C-Mo/CB. (d) EDS mapping of Mo and C elements in Mo2C-Mo/CB.
Figure 3. (a) TEM image of the Mo2C-Mo/CB catalyst. (b) The statistics of Mo2C-Mo/CB particle size distribution. (c) HRTEM image of the interface between Mo2C (101) and Mo (110) in Mo2C-Mo/CB. (d) EDS mapping of Mo and C elements in Mo2C-Mo/CB.
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Figure 4. XPS spectra of Mo2C-Mo/CB. (a) Mo 3d region and (b) C 1s region.
Figure 4. XPS spectra of Mo2C-Mo/CB. (a) Mo 3d region and (b) C 1s region.
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Figure 5. (a) Linear sweep voltammetry curves of bare carbon paper, commercial Mo2C and Mo2C-Mo/CB in 0.5 M H2SO4 without iR compensation. (b) Tafel plots of commercial Mo2C and Mo2C-Mo/CB. (c) Linear sweep voltammetry curves of Mo2C-Mo/CB before and after 1000 cycles of cyclic voltammetry in 0.5 M H2SO4 without iR compensation. (d) Nyquist plots of commercial Mo2C and Mo2C-Mo/CB recorded at −0.24 V vs RHE in 0.5 M H2SO4.
Figure 5. (a) Linear sweep voltammetry curves of bare carbon paper, commercial Mo2C and Mo2C-Mo/CB in 0.5 M H2SO4 without iR compensation. (b) Tafel plots of commercial Mo2C and Mo2C-Mo/CB. (c) Linear sweep voltammetry curves of Mo2C-Mo/CB before and after 1000 cycles of cyclic voltammetry in 0.5 M H2SO4 without iR compensation. (d) Nyquist plots of commercial Mo2C and Mo2C-Mo/CB recorded at −0.24 V vs RHE in 0.5 M H2SO4.
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Figure 6. (a) Capacitive current densities of commercial Mo2C and Mo2C-Mo/CB plotted against scan rates. (b) Normalization of the geometric current density with active site concentration at an overpotential of 300 mV. Because of the unknown capacitive behavior (Cs) of the Mo2C, active site activity*Cs was employed to compare the intrinsic activity.
Figure 6. (a) Capacitive current densities of commercial Mo2C and Mo2C-Mo/CB plotted against scan rates. (b) Normalization of the geometric current density with active site concentration at an overpotential of 300 mV. Because of the unknown capacitive behavior (Cs) of the Mo2C, active site activity*Cs was employed to compare the intrinsic activity.
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MDPI and ACS Style

Zhang, H.; Qi, S.; Zhu, K.; Wang, H.; Zhang, G.; Ma, W.; Zong, X. Ultrafast Synthesis of Mo2C-Based Catalyst by Joule Heating towards Electrocatalytic Hydrogen Evolution Reaction. Symmetry 2023, 15, 801. https://doi.org/10.3390/sym15040801

AMA Style

Zhang H, Qi S, Zhu K, Wang H, Zhang G, Ma W, Zong X. Ultrafast Synthesis of Mo2C-Based Catalyst by Joule Heating towards Electrocatalytic Hydrogen Evolution Reaction. Symmetry. 2023; 15(4):801. https://doi.org/10.3390/sym15040801

Chicago/Turabian Style

Zhang, Hefeng, Shengliang Qi, Kaixin Zhu, Haidong Wang, Guanghui Zhang, Weiguang Ma, and Xu Zong. 2023. "Ultrafast Synthesis of Mo2C-Based Catalyst by Joule Heating towards Electrocatalytic Hydrogen Evolution Reaction" Symmetry 15, no. 4: 801. https://doi.org/10.3390/sym15040801

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