| Cite this article as: |
Shaorou Ke, Yajing Zhao, Xin Min, Yanghong Li, Ruiyu Mi, Yangai Liu, Xiaowen Wu, Minghao Fang, and Zhaohui Huang, Highly mass activity electrocatalysts with ultralow Pt loading on carbon black for hydrogen evolution reaction, Int. J. Miner. Metall. Mater., 32(2025), No. 1, pp.182-190. https://dx.doi.org/10.1007/s12613-024-2912-x
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Pt-based nanocatalysts offer excellent prospects for various industries. However, the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge. In this study, nanocatalysts with ultralow Pt content, excellent performance, and carbon black as support were prepared through in-situ synthesis. These ~2-nm particles uniformly and stably dispersed on carbon black because of the strong s–p–d orbital hybridizations between carbon black and Pt, which suppressed the agglomeration of Pt ions. This unique structure is beneficial for the hydrogen evolution reaction. The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction, exhibiting a potential of 100 mV at 100 mA·cm−2, which is comparable to those of commercial Pt/C catalysts. Mass activity (1.61 A/mg) was four times that of a commercial Pt/C catalyst (0.37 A/mg). The ultralow Pt loading (6.84wt%) paves the way for the development of next-generation electrocatalysts.
Hydrogen production mainly relies on the performance of electrocatalysts used during the electrochemical splitting of water. Platinum (Pt) is considered the most promising among materials for hydrogen evolution reaction (HER) [1–2] because of its empty d orbitals that can effectively form coordination bonds [3–5] and its unique structure with strong adsorption capabilities [6–8]. Non-Pt electrocatalysts, such as molybdenum- and nickel-based catalysts [9–11], have potential industrial applications. However, a large performance gap has been found between state-of-the-art Pt-based and non-Pt catalysts. Owing to the scarcity of noble metal resources [12], the development of highly efficient catalysts with high mass activity and low Pt-loading or non-Pt alternatives is of great practical significance [13–15].
Among various types of catalysts, supported catalysts can load active components onto a support. This process not only increases the specific surface area but also effectively reduces the amount of Pt used, resulting in high mass active catalysts with low loading. The catalytic activity of supported catalysts is closely related to the particle size and dispersion of the active component Pt [16–17]. By adopting different synthesis methods and adjusting various synthesis conditions [18–20], the active component Pt can be reduced to the nanoscale level and even to the single-atom level. Research on single-atom catalysts (SACs) has focused on designing catalysts with high mass activity while minimizing the use of noble metals [21]. Strategies such as doping to regulate metal–support interactions can yield excellent catalytic performance [22–23], although their mass activity remains controversial [24–25]. The dispersion of single atoms is difficult to maintain because of the Gibbs–Thomson effect [26] and strong covalent metal–support interaction [27] in SACs [28]. Single atoms tend to aggregate into nanoclusters, which in turn limit the development of single atom-supported catalysts [29]. However, supported catalysts with active components in the form of nanoclusters are more stable and less prone to migration and agglomeration [2,30]. Compared with Pt transition metal alloy nanocatalysts with dense structures [31], Pt nanocatalysts are not limited by mass transport, can achieve higher atomic utilization, and demonstrate high intrinsic activity [32]. Li et al. [1] have obtained stable nanocatalysts with Pt supported on MoS2 through a thermal annealing process. However, high-temperature synthesis can lead to the crystal growth of Pt, limiting the performance of the nanocatalysts. Nevertheless, nanoscale supported catalysts prepared through in-situ synthesis [33–37] undergo charge density redistribution during high-temperature in-situ synthesis. This process is beneficial for obtaining Pt with a rich electronic structure [15]. The high mass activity of Pt nanoscale supported catalysts is attributed to the rapid charge transfer from Pt clusters to the support [38]. Therefore, Pt nanocatalysts prepared by in-situ reduction not only address the issue of crystal growth under high-temperature synthesis conditions [39] but also yield catalysts with high mass activity. The current in-situ reduction process is relatively complex. Therefore, developing a simple preparation strategy is crucial to the preparation of novel catalysts with high mass activity and ultralow Pt loading.
Ultrasonic disruption and in-situ carbothermal reduction are utilized for catalyst preparation. Ultrasonic disruption ensures the uniform distribution of Pt and promotes the migration of Pt ions [40]. It prevents the instability of coordination structures during the carbothermal reduction process. Meanwhile, carbon black (CB) is used as a support to anchor Pt species, effectively limiting their overgrowth [41–42]. The self-prepared Pt/C catalysts with ultralow Pt content exhibit excellent mass activity and stability for HER. This excellent performance is attributed to the high conductivity of CB and the highly active Pt sites. The covalent bonds between Pt and carbon, along with the sp2–sp3 hybridized bonds between C–C, undergo strong s–p–d orbital hybridization, facilitating the transfer of electrons from carbon to Pt. Given the ultralow loading of Pt and high mass activity, the catalysts obtained through ultrasonic disruption and in-situ carbothermal reduction are promising electrocatalysts for hydrogen production.
All chemicals utilized in this research, such as CB and chloroplatinic acid (H2PtCl6·H2O), were used without any further purification.
A series of Pt/C catalysts were synthesized by ultrasonic disruption and in-situ reduction. For the preparation of the Pt/C catalysts, CB (0.12 g) was dispersed in 10 mmol/L H2PtCl6·H2O and sonicated for 6 min at 60% power (the process was performed for 3 s between 9 s intervals). Then, the mixture was transferred to a 50 mL microtube for centrifugation and dried at 60°C for 12 h in a vacuum oven. The as-prepared composite was calcinated at 600°C for 2 h in a tube furnace under Ar atmosphere. The temperature was increased at a rate of 2°C/min.
The crystallinity of the samples was determined by X-ray diffraction (XRD, Buker D8 Advance) in Bragg angles (2θ) from 10° to 80°. The morphology of the samples was characterized through transmission electron microscopy (TEM, FEI Tecnai G2 F30) and high-resolution TEM (HRTEM, FEI Tecnai G2 F20). Then, the chemical states of various elements in the samples were analyzed through X-ray photoelectron spectroscopy (XPS, Escalab 250 Xi), and the Pt content in the catalysts was measured with an inductively coupled plasma-optical emission spectrometer (ICP-OES, PerkinElmer 8300).
The hydrogen generation performance of the catalysts was examined by CHI760e. All electrochemical tests, including linear sweep voltammetry (LSV) and cyclic voltammetry (CV), were conducted in 0.5 M H2SO4 solution for three-phase electrode electrochemical measurements. LSV was conducted at a scanning rate of 10 mV/s within a potential range of −0.08 to −0.44 V. The stability of the samples was assessed by comparing the LSV test results before and after 2000 cycles CV and chronoamperometric testing for 20 h. All measured potentials were calibrated as reversible hydrogen electrodes (RHEs) according to the following equation:
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ERHE=EAg/AgCl+Etest+0.059×pH |
(1) |
The diffusion of H2 was accelerated through the iR correction of the LSV for the HER with 80% iR compensation. The correction was calculated by the following equation:
|
Ecorrected=Emeasured−iR |
(2) |
The Tafel slope of all samples was determined using the following equation:
|
η=b×lg|j|+a |
(3) |
where j is the current density of the sample, η is the overpotential at the current density of j, b is the Tafel slope of the sample, and a is the Tafel constant.
The catalytic activity of the Pt clusters on carbon was evaluated through computational studies, which were conducted using the Vienna ab initio simulation package (VASP 5.4.4). The Perdew–Burke–Ernzerhosf was adopted to describe the exchange-correlation energy [43]. A cutoff energy of 400 eV was used for the plane wave expansion, and the Brillouin-zone integration was set at a k-mesh of 3 × 3 × 3. The energy convergence criterium for atomic structures was 10−4 eV/atom, and the convergence threshold for the forces was 0.01 eV/Å. The Gibbs free energy was calculated after the vibration frequencies for each H dissociation step were obtained. The appearance of imaginary frequencies was prevented by using the VASPKIT postprocessing tool.
The synthesis of the self-prepared Pt/C is illustrated in Fig. 1. Initially, [PtCl6]2+ and H+ were dissociated on CB. Second, the powder was obtained after ultrasonic disruption, centrifugation, and drying. The chloroplatinate ions fully permeated the CB through diffusion [34] and stably combined with CB, preventing the loss of noble metal ions after centrifugal washing and thereby improving atomic utilization efficiency (AUE). Finally, the powders were calcined in a tube furnace for in situ carbothermal reduction and the anchoring of platinum ions.
The composition and structure of the electrocatalyst were studied, revealing that the Pt4+ was successfully reduced to Pt. In the XRD patterns (Fig. 2(a)), the broad diffraction peak at 23° was from CB with low graphitization (Figs. S1–S3), whereas the sharp diffraction peaks at 39.8°, 46.3°, and 67.5° were derived from Pt (PDF No. 4-802). In TEM, the Pt nanoparticles (NPs) dispersed uniformly on the support are visible (Fig. 2(b)). According to HRTEM, the spacing of the lattice fringe (d) was 0.22 nm, which corresponded to Pt (111) and further confirmed that Pt was prepared through carbothermal reduction (Fig. 2(c)). The Pt NPs had a diameter of (2.06 ± 0.36) nm (Fig. 2(d)), which were the smallest and most uniformly dispersed (Fig. S4). The ICP-calculated Pt content in the self-prepared Pt/C was approximately 6.82wt%, which was lower than those of the other catalysts (Table S1). The optimal Pt NP content will enhance HER performance and improve the AUE. XPS analysis further indicated the presence of Pt. C 1s spectra exhibited three binding energies, namely, C–C (aromatic group), C–C (aliphatic group), and O–C=O, corresponding to 284.77, 285.40, and 289.22 eV, respectively [44] (Fig. 2(e)). No significant difference with C 1s prepared under other conditions was observed (Figs. S5–S13). The XPS spectrum of Pt 4f (Fig. 2(f)) indicated that Pt was reduced. The peaks at 71.62, 75.01, 72.90, and 76.10 eV were derived from Pt0 and Pt2+ [45]. The reduced metallic Pt contained more, which can have better performance in catalytic reactions (Table S2).
To investigate the interface differences between self-prepared and commercial Pt/C, the XPS of commercial Pt/C and CB were tested. The results showed no significant difference among the C 1s spectra of self-prepared Pt/C, commercial Pt/C, and CB, which contained aromatic C–C, aliphatic C–C, and O–C=O (Fig. S14). This result indicated that the addition of Pt and the difference in preparation methods did not affect carbon itself. However, a comparison of the Pt 4f spectra revealed that self-prepared Pt/C contained Pt in the 0 and 2+ states, whereas commercial Pt/C contained Pt in the 0 and 4+ states (Fig. S15), possibly because of differences in the preparation processes, which resulted in the different valence states of Pt. Additionally, by comparing the binding energy values under the same conditions, the binding energy of commercial Pt/C was generally higher than that of the self-prepared Pt/C. This result indicated a decrease in the electron cloud density around commercial Pt/C, decreasing the probability that electrons will appear between carbon and Pt, simultaneously causing an increase in the nuclear spacing and a decrease in molecular stability. Therefore, the self-prepared Pt/C prepared in this experiment exhibited better catalytic stability than commercial Pt/C. The scanning transmission electron microscopy-coupled energy-dispersive X-ray spectroscopy (STEM-EDS) elemental mapping (Fig. 2(g)–(i)) confirmed that the Pt NPs were uniformly distributed on the surface of CB.
Pt/C samples synthesized with varying impregnation concentrations and different carbothermal reduction temperatures were thoroughly studied. Pt NPs were stably supported on CB (Figs. S16–S23) and dispersed uniformly. When the concentration of the solution increased from 5 to 15 mmol/L, the sizes of the Pt NPs increased slightly from 2.22 to 2.24 nm. This increase indicated that the concentration of H2PtCl6·H2O was not the main factor affecting the Pt NPs. However, the temperature influenced particle size. When the temperature increased from 400 to 800°C, the sizes of the Pt NPs increased from 2.49 to 2.60 nm. Low heat treatment temperatures reduced the thermal motion of [PtCl6]2−, promoting collisions among adjacent ions. Furthermore, owing to the weak thermal motion of ions, the formed Pt metal NPs were mainly concentrated at the edges of the support and did not achieve good dispersion. An increase in heat treatment temperature enhanced the thermal motion among ions, facilitating the uniform dispersion of Pt on CB. However, high heat treatment temperatures can increase the probability of collision among ions and enhance the nucleation and growth of Pt. Under various conditions, the sizes of Pt NPs were all within a range of 2–3 nm during ultrasonic in-situ reduction. These NPs will provide active sites for electrochemical reactions. Raman analysis results showed that the R value (defined as the intensity ratio of the D peak to the G peak) continuously decreased (from 2.15 to 1.80) with increasing temperature, demonstrating that the degree of graphitization of CB increases. Thus, the conductivity of the catalysts increased, and electron transfer proceeded (Fig. S24) [46]. An increase in temperature facilitated the reduction of Pt (Figs. S5–S13). Although the preparation conditions varied, the Pt content in the self-prepared Pt/C catalysts was extremely low (Table S3), obtaining large AUE. As the concentration of H2PtCl6·H2O increased, the mass fraction of Pt in Pt/C showed a gradually increasing trend (from 5.23wt% to 8.00wt%). As the temperature increased, the mass fraction of Pt in Pt/C increased from 4.10wt% to 10.60wt% (Table S1).
The HER performance of the self-prepared Pt/C was tested in a 0.5 M H2SO4 solution. Commercial Pt/C catalysts were tested under the same conditions. The self-prepared Pt/C was impregnated in a 10 mmol/L H2PtCl6 solution and heated at 600°C. It exhibited the best HER performance (Fig. S25). The overpotential was 100 mV versus the RHE (100 mA·cm−2), indicating that the concentration of Pt was not associated with catalyst activity. However, this work demonstrated a similar catalyst activity to commercial Pt/C (105 mV at 100 mA·cm−2) under a low concentration of Pt (6.82wt% and 20wt%, respectively; Fig. 3(a)). This catalyst exhibited a similar Tafel slope (37 mV·dec−1) to a commercial Pt/C catalyst (34 mV·dec−1; Fig. 3(b)), indicating that Volmer–Tafel process was the main HER mechanism. Further analysis indicated that the HER reaction is a process with a controllable hydrogen ion diffusion rate [47] (Fig. S26). The mass activity of the self-prepared Pt/C was 1.61 A/mg at –0.05 V versus RHE, which was higher than those of the other prepared (Fig. S27) and 1.24 A/mg higher than that of commercial Pt/C catalysts (Figs. 3(c) and S28) [48]. The Pt/C catalysts prepared in a 10 mmol/L H2PtCl6 solution and heated at 600°C showed large electrochemically active surface area mainly because of the reduced Pt NP size and Pt loading [49] (Fig. S29).
Under this condition, the Tafel slope and overpotential of the prepared Pt/C catalysts exhibit better performance (Fig. 3(d) and (e)) than those of the Pt/C catalysts prepared in other carbon substrates [50–68], demonstrating more effective atom utilization because of their lower Pt content (Table S1). The possible reason for this difference is the preparation process and structure. On the one hand, CB has a larger interlayer spacing than graphite. It has high conductivity and oxidation resistance, providing favorable conditions for Pt NPs [69]. On the other hand, the high energy provided by ultrasonic disruption increases CB activity. An in-situ method reduces the movement of platinum ions and efficiently improves Pt atom utilization.
To assess the stability of the self-prepared Pt/C catalysts, continuous long-term CV and chronoamperometry tests were conducted. After 2000 cycles of CV, the attenuation of self-prepared Pt/C catalysts (1.3 mV at 50 mA·cm−2) was notably lower than that of commercial Pt/C catalysts (34.0 mV at 50 mA·cm−2; Fig. 3(f)). The chronoamperometry curves (i–t curves) of the self-prepared Pt/C catalysts were plotted at a constant potential of −0.2 V for 20 h. It exhibited a minimal current drop (~12%), which was better than that of the commercial Pt/C catalysts (~25%; Fig. 4(a)), indicating excellent electrochemical stability. Furthermore, the underlying cause of performance decay in the self-prepared and commercial Pt/C catalysts after stability testing was investigated through HRTEM analysis (Fig. 4(b) and (c)) and STEM-EDS (Fig. 4(d)–(f)). After stability testing, the Pt particles in the self-prepared Pt/C catalysts remained uniformly distributed on the carbon support, whereas the commercial Pt/C catalysts showed severe agglomeration. Additionally, particle size analysis was performed. The self-prepared Pt/C catalysts were approximately 1.25 nm in size, suggesting that the inevitable Ostwald ripening phenomenon occurred in the catalysts and led to the dissolution of small particles (Fig. S30).
Combined with DFT calculations, the study discusses the excellent electrocatalytic activity of the self-prepared Pt/C catalysts in HER. Fig. 5(a) displays the optimized calculation model, and the schematic diagram of the c-axis direction is shown in Fig. S31. The differential charge density (Δρ; Fig. 5(b)) and average Δρ in a combination of Bader charge analysis showed that approximately 0.086745 electrons per supercell migrated from C to Pt, suggesting an improved environment for catalyzing the electrochemistry of water [4]. In HER, low hydrogen adsorption free energy (ΔG∗H) results in exceptional H∗ads adsorption strength [70–71]. The ΔG∗H was calculated under the model after the adsorption of H (Fig. S32). The results showed that the ΔG∗H value of the self-prepared Pt/C catalysts (−0.339 eV) was more favorable than those of other catalysts (pure carbon and pure Pt) and exhibited a smaller negative Gibbs free energy, indicating the potential of the self-prepared Pt/C catalysts as HER electrocatalysts (Fig. 5(c)).
The geometry optimization model of the self-prepared Pt/C catalysts showed that the Pt atoms were positioned on bridge sites between carbon atoms (Fig. 5(a)). Compared with pure carbon, the carbon in a self-prepared Pt/C catalyst exhibited an undulated structure because of the formed covalent bond between the Pt and carbon atoms. The C–C bond length near the carbon loaded with Pt (Table S4) was between the bond lengths of graphite and diamond (1.420 and 1.544 Å, respectively), which have sp2–sp3 bonds [72]. Owing to mixed bonding, carbon atoms in the self-prepared Pt/C catalysts had a sp2–sp3 alternating bond configuration [73]. The strong s–p–d orbital hybridization between the carbon substrate and Pt cluster resulted in excellent catalytic performance. In addition, the density of states (DOS) showed that the prepared catalysts exhibited metallic properties because the wave of Pt crossed the Fermi level (Fig. 5(d)). The Pt and C orbitals resulted in orbital overlap, which indicated adsorption between surface Pt clusters and support surface [74]. All these characteristics simultaneously enhanced HER performance, suggesting the potential of low contents of Pt as an HER electrocatalyst.
To maximize the utilization of a noble metal, the design of ultralow noble metal loading catalysts often involves the use of carbon materials. We have demonstrated that the content and size of Pt can affect the activity of Pt/C catalysts toward HER. The kinetics of HER can be controlled to achieve high activity through integrated strategies, including ultrasonic disruption and in-situ carbothermal reduction. The results indicated that ultralow Pt (6.82wt%) NPs with 2.06 nm particle size were dispersed uniformly on CB. The relative overpotential at 100 mA·cm−2 was only 100 mV, and the Tafel slope was 37 mV·dec−1. The HER performance of the prepared catalysts is similar to that of commercial Pt/C catalysts. The mass activity (1.61 A/mg) was four times that of commercial Pt/C catalysts. The facile, universality, and wide applicability of this strategy can be further used in the preparation of ultralow Pt-based catalysts. A new approach is proposed in our work to produce catalysts with low loading content for highly active HER.
This work was financially supported by the National Natural Science Foundation of China (No. 5217042069), the Young Elite Scientist Sponsorship Program by China Association for Science and Technology (CAST) (No. YESS20200103), and the Fundamental Research Funds for the Central Universities (No. 265QZ2022004).
The authors declare no conflict of interest.
The online version contains supplementary material available at https://doi.org/10.1007/s12613-024-2912-x.
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