Pt/C catalysts containing CeO2 with different morphologies for the hydrogen evolution reaction

doi:10.21203/rs.3.rs-3210000/v1

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Pt/C catalysts containing CeO2 with different morphologies for the hydrogen evolution reaction

https://doi.org/10.21203/rs.3.rs-3210000/v1

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Pt/C catalysts containing four different morphologies of CeO₂ as co-catalysts were synthesized in this work, and their electrocatalytic performance for hydrogen evolution reaction (HER) was investigated. As compared with the Pt/C catalyst, these four catalysts containing CeO₂ all exhibited improved catalytic activity. Among them, the Pt/C catalyst containing spherical CeO₂ with a diameter of 30 ~ 60 nm (Pt/C-CeO₂(s₂)) possesses the best catalytic activity, displaying an over-potential of 258 mV at 10 mA cm^− 2 and a Tafel slope of 42 mV dec^− 1. According to the characterization results of structure, morphology and elemental valence state, the enhancement of catalytic activity is ascribed to the small particle size and good dispersion degree of Pt, as well as the strong interaction between the exposed (111) crystal plane of small spherical CeO₂ and Pt, which leads to a significant increase in metallic Pt content. Moreover, the Pt/C-CeO₂(s₂) catalyst also demonstrates outstanding long-term stability besides exceptional catalytic activity. The results clearly illustrate that CeO₂ with diverse shapes and sizes can remarkably influence the catalytic performance of loaded Pt particles in the HER process.

CeO2

Electrocatalysts

Hydrogen Evolution Reaction

Morphologies

The massive development and utilization of fossil fuels have brought a series of environmental problems, and thus a sustainable and green energy source is in demand urgently [1, 2]. As a kind of energy carrier with advantages of wide sources and pollution-free products, hydrogen has received much attention [3, 4]. Water electrolysis is believed to be the most promising technology for obtaining high-purity hydrogen, which is safe and efficient and has no pollutant emissions [5–7]. Overall, it involves two half-cell reactions, namely, the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) [8]. However, the slow kinetics of the OER and HER necessitates a large cell voltage, which requires a large electrical input and incurs a high cost. This impedes the commercialization of water electrolysis technology for hydrogen production [9]. Therefore, it is necessary and urgent to develop highly active and stable catalysts for the OER and HER. It is well known that the noble metal Pt is considered as the most efficient catalyst for HER due to its low over-potential and enhanced electrocatalytic stability [10, 11]. Nevertheless, the scarcity and high cost of Pt limit its practicality [12]. Recently, various non-noble metal electrocatalysts have been extensively studied for HER, such as molybdenum-based [6, 9, 13, 14], iron-based [15, 16], cobalt-based [17, 18] and nickel-based catalysts [19, 20], and so on. However, although the performance of these non-noble metal electrocatalysts has been significantly improved, the catalytic activity of the vast majority of them is still obviously lower than that of Pt/C.

Cerium oxide (ceria, CeO₂) is one of the most abundant rare-earth oxides, and it plays an important role as a carrier of an active phase or as a co-catalyst in many catalytic processes [21–27]. In our previous work [28], it was found that the addition of CeO₂ into Pd/C catalysts could remarkably improve the catalytic performance for formic acid electro-oxidation in terms of current density, peak potential and kinetics. In addition, it was reported that strong metal-oxide interactions exist between CeO₂ and Pt, which can modulate the intrinsic electronic structure of Pt and thus enhance the catalytic performance for CO oxidation in a H₂-rich gas [29]. Moreover, different shapes of CeO₂ may have different effects on the interaction between CeO₂ and Pt [30], as different shapes can lead to different exposed crystal planes. This indicates that the co-catalytic effect of CeO₂ is somewhat related to its shape. Additionally, the size of CeO₂ particles is another factor that influences the catalytic activity of Pt particles supported by them. Vayssilov et al. confirmed that the electronic structure of Pt atoms was radically changed after being dispersed on nano-CeO₂ [31]. Hence, it can be seen that the morphology (including shape and size) of CeO₂ has an important influence on its interaction with metals and catalytic performance. However, to our knowledge, the application of CeO₂ with different morphologies as co-catalysts to retouch the Pt/C catalyst for HER has not been reported. In this work, the Pt/C catalysts modified with four different morphologies of CeO₂ were synthesized, and their catalytic performance for HER was investigated. These four catalysts all exhibited better catalytic performance than Pt/C, and the effects of CeO₂ with different morphologies were analyzed in detail. The results are helpful to understand the role of metal-oxide interactions in the electrocatalytic performance of Pt-based catalysts. Furthermore, the improvement of Pt/C catalyst performance also has important economic significance for the commercialization of hydrogen production by water electrolysis.

Synthesis of carbon black-supported Pt-CeO₂ with different morphologies

To synthesize the catalysts, the carbon black (Vulcan XC-72) was firstly dispersed into deionized water (or water-ethanol binary mixtures) and then the mixture was sonicated for 15 min. Then cerium nitrate hexahydrate and polyvinyl pyrrolidone (PVP) were added into the suspension with stirring thoroughly for 0.5 h. The suspension was subjected to hydrothermal heating at 180°C for 30 hours. Subsequently, a certain amount of potassium chloroplatinate and trisodium citrate were put into the above mixture. After that, an excess of freshly prepared sodium borohydride solution was added dropwise and stirred for 6 h at room temperature. Finally, the resulting products were filtered, washed and dried in an oven at 60°C to obtain carbon black-supported Pt catalysts with spherical CeO₂. By changing PVP in the raw materials into sodium hydroxide and trisodium citrate, carbon black-supported Pt catalysts with cubic CeO₂ (or irregular polyhedral CeO₂) were prepared. The theoretical loadings of Pt and CeO₂ in these Pt/C-CeO₂ catalysts are 20 and 10 wt%, respectively.

Materials characterization

X-ray diffraction (XRD, Smart Lab (9 kW), Cu Kα) was conducted to analyze the phase composition and crystal structure of the catalysts. The morphology of the materials was analyzed by transmission electron microscopy (TEM, TECNAIG 20) and high resolution transmission electron microscopy (HRTEM, JEM2100F). X-ray photoelectron spectroscopy (XPS, ESCALAB 250Xi) was used to analyze the elemental species as well as valence information on the material surface.

Electrochemical Measurement

The electrochemical measurements were performed using a three-electrode cell with an electrochemical workstation (CHI760D, Chenhua, Shanghai) and the electrolyte was 0.5 M H₂SO₄ saturated with N₂. A platinum electrode was used as the counter electrode, and a saturated calomel electrode was used as the reference electrode. To prepare a catalyst-modified work electrode, 4 mg catalyst was dispersed into 2 mL anhydrous ethanol, and then 5 µL of the suspension was added to the surface of a glassy carbon electrode after ultrasonic dispersion, and finally the catalysts were fixed with 2 µL of 0.5% Nafion after the ink was dried. All potentials were calibrated to the reversible hydrogen electrode: E (vs RHE) = E (vs SCE) + 0.0592 pH + 0.242 V = E (vs SCE) + 0.242 V (pH = 0).

Linear sweep voltammetry (LSV) was tested from 0 to -0.6 V in 0.5 M H₂SO₄ solution with a scan rate of 50 mV s^− 1 after the activation process. The cyclic voltammograms (CVs) were measured from − 0.15 to -0.03 V at different scan rates (from 20 to 200 mV s^− 1, interval is 20 mV s^− 1) for obtaining the electrical double layer capacitances (C_dl). The stability test was carried out by CV scanning for 1000 revolutions with a scan rate of 50 mV s^− 1.

TEM and HRTEM images of Pt/C-CeO₂ with different morphologies are shown in Fig. 1, and it can be seen that these CeO₂ particles exhibit clear but various features. In Fig. 1a₁ and b₁, CeO₂ is nearly spherical, while CeO₂ in Fig. 1c₁ and d₁ has a cubic and irregular polyhedral shape (although a few particles present a rhombic hexahedron shape), respectively. This shape difference mainly stems from the difference in the raw materials of the synthesis process. Furthermore, it is obvious that the CeO₂ particle sizes in Fig. 1a₁ and c₁ are markedly larger than those in Fig. 1b₁ and d₁. Specifically, the diameters of CeO₂ spheres in Fig. 1a₁ and b₁ are 225 ± 25 nm and 30 ~ 60 nm, respectively. Similarly, the edge lengths of CeO₂ cubes and irregular polyhedrons in Fig. 1c₁ and d₁ are approximately 200 nm and 80 ~ 180 nm, respectively. Under the same raw materials and thus the similar shape, the differences of particle sizes result from different synthesis media. The large and small particles were synthesized in the deionized water and water-ethanol binary mixtures, respectively. In other words, with the increase of ethanol, the particle size of CeO₂ becomes smaller. It is inferred that when the volume ratio of ethanol-water rises, the solubility of the reactants decreases, resulting in a higher supersaturation. This elevated supersaturation affects the nucleus growth period, namely, causing it to be shortened. As a result, the size of CeO₂ becomes smaller [32]. For the convenience of the statement, these catalysts in Fig. 1a₁, b₁, c₁ and d₁ are denoted as Pt/C-CeO₂(s₁), Pt/C-CeO₂(s₂), Pt/C-CeO₂(c) and Pt/C-CeO₂(p), respectively.

As reported previously [30, 32] and revealed by the HRTEM images (Fig. 1 a₂-d₂), the (111) crystal plane is exposed by the spherical CeO₂ selectively, and the (200) crystal plane is exposed by the cubic CeO₂ selectively. However, Pt/C-CeO₂(p) has different exposed crystal planes, such as (200) and (220) planes (Fig. 1-d₂), which may be due to various shapes of CeO₂ in this sample. The decoration of Pt nanoparticles can be observed on carbon black and/or CeO₂ surfaces with a typical interplanar spacing of 0.23 nm, which is attributed to the (111) plane of Pt.

The XRD patterns in Fig. 2 demonstrate the successful synthesis of Pt/C-CeO₂ with different morphologies. According to our previous work [33], the Pt/C catalyst was also prepared for comparison and its XRD pattern is displayed in Fig. 2, too. The peaks at 25° in all the XRD patterns are ascribed to the (002) plane of carbon black support. The diffraction peaks located at 28.5°, 33.1°, 47.5°, 56.3°, 59.1°, 69.4°, 76.7° and 79.1°correspond to (111), (200), (220), (311), (222), (331), (420) and (422) planes of CeO₂ (JCPDF#81–0792), respectively. The diffraction peaks located at 39.9°, 46.4°, 67.7° and 81.6° are assigned to the (111), (200), (220), and (311) planes of Pt (JCPDF#87–0640), respectively. The particle sizes of Pt in Pt/C-CeO₂(s₁), Pt/C-CeO₂(s₂), Pt/C-CeO₂(c), Pt/C-CeO₂(p) and Pt/C are calculated to be 3.36, 2.98, 4.27, 5.22, 5.48 nm using the Scherrer’s equation d = 0.89λ/βcosθ, respectively. Notably, Pt nanoparticles in the four catalysts containing CeO₂ are smaller than those in Pt/C. Moreover, the Pt diffraction peaks of Pt/C-CeO₂ (s₁) are narrower as compared to those of Pt/C-CeO₂(s₂), which is consistent with the result that Pt/C–CeO₂(s₁) has a larger particle size of Pt. A similar trend is observed for Pt/C-CeO₂(p) and Pt/C-CeO₂(c).

The dispersion degree and the particle size distribution of Pt in the four catalysts containing CeO₂ can be clearly observed in Fig. 3. Specifically, Pt/C-CeO₂(s₁), Pt/C-CeO₂(s₂) and Pt/C-CeO₂(c) exhibit more uniform dispersions, which are superior than Pt/C compared to our previous work [33], while Pt/C-CeO₂(p) shows more severe agglomeration. It is well-known that the dispersion of catalytic active sites plays a crucial role in improving the electrochemical active surface area and catalyst utilization. In addition, it is evident that the particle size distribution of Pt in these four catalysts (Fig. 3a₂-d₂) almost corresponds to the Pt particle sizes calculated from Scherrer’s equation in the XRD patterns (Fig. 2).

Figure 4 displays the high-resolution XPS spectra of Pt 4f for Pt/C-CeO₂ with different morphologies and Pt/C. Taking the Pt/C-CeO₂(s₂) as an example (Fig. 4a), on the fitting curves, the most intense peaks (70.60 and 73.87 eV) are the characteristics of Pt⁰, and the second and weaker doublet (71.25 and 74.68 eV) can be assigned to Pt²⁺ [34–37]. Furthermore, the Pt binding energy of all four catalysts containing CeO₂ demonstrates a negative shift compared to the Pt/C catalyst in Fig. 4a and b, suggesting an increase in the content of low-valence Pt species. The binding energy (B.E.) and relative intensity of Pt species in the five catalysts are exhibited in Table 1 by fitting calculation, which shows that the order of Pt⁰ content is Pt/C-CeO₂(s₂)> Pt/C-CeO₂(s₁)> Pt/C-CeO₂(c)> Pt/C-CeO₂(p)> Pt/C. Figure 4c reveals the high-resolution XPS spectra of Ce 3d for Pt/C-CeO₂ with different morphologies. The Ce 3d spectra are divided into eight peaks [38]. Among them, the peaks u and u' located at 906.64 eV and 885.86 eV are attributed to Ce³⁺, and the other peaks are assigned to Ce⁴⁺. CeO₂ has a fluorite structure, where the cation valence state can be switched between Ce³⁺ and Ce⁴⁺ [39, 40]. Additionally, the relative intensity of Ce species in the four catalysts is listed in Table 2, which displays that the order of Ce⁴⁺ content is Pt/C-CeO₂(s₂)> Pt/C-CeO₂(s₁)> Pt/C-CeO₂(c)> Pt/C-CeO₂(p). It is interestingly found that the order of Ce⁴⁺ content is exactly the same as that of Pt⁰ content. In other words, the more Ce⁴⁺, the more Pt⁰. For Pt/C, the content of Pt⁰ is the lowest since it does not contain CeO₂. This indicates the “metallization” effect of CeO₂ on Pt, which may be ascribed to the electrostatic interaction between CeO₂ and Pt. It is well known that Pt has a valence electron configuration of 4f¹⁴5d⁹6s¹, which contains unoccupied orbits, but the valence electron configuration of Ce³⁺ is 4f¹, namely betatopic configuration. Thus, the electrons of Ce³⁺ may have a trend to transfer to Pt, leading to an increase of Pt⁰ and Ce⁴⁺. This reveals the reason for the consistent order of Pt⁰ and Ce⁴⁺ content in these four catalysts containing CeO₂. In addition, it has been reported that the (111) crystal plane is more likely to lose electrons than the (200) and (220) crystal planes in CeO₂ owing to different O-vacancy concentrations in different crystal planes [41]. Therefore, Pt/C-CeO₂(s₁) and Pt/C-CeO₂(s₂) contain more Pt⁰ than Pt/C-CeO₂(c) and Pt/C-CeO₂(p) because the CeO₂ in the former two is nearly spherical, mainly exposing the (111) crystal plane, according to TEM and HRTEM images (Fig. 1). Furthermore, the large discrepancy of CeO₂ particle size between Pt/C-CeO₂(s₁) and Pt/C-CeO₂(s₂) (Fig. 1a₁ and 1b₁) results in significant differences in the Pt⁰ content between them. For Pt/C-CeO₂(s₂), a much smaller particle size of CeO₂ inevitably leads to a significant increase in the contact surface between Pt and CeO₂, thereby strengthening their interaction and increasing the Pt⁰ content. However, this phenomenon does not exist between Pt/C-CeO₂(c) and Pt/C-CeO₂(p) despite a smaller particle size of CeO₂ in the latter one because CeO₂(200) plane is easier to lose electrons than CeO₂(220) plane [41], and thus Pt/C-CeO₂(c) (exposing (200) planes) contains a higher Pt⁰ content than Pt/C-CeO₂(p) (mainly exposing (220) planes, with few (200) planes).

Table 1

Binding energy (B.E.) and relative intensity of Pt species in four Pt/C-CeO₂ with different morphologies as well as Pt/C.
Catalysts	Species	B.E. of Pt 4f_7/2 (eV)	B.E. of Pt 4f_5/2 (eV)	Relative intensity (%)
Pt/C-CeO₂(s₁)	Pt⁰	71.39	74.77	51.28%
	Pt²⁺	71.88	75.98	48.72%
Pt/C-CeO₂(s₂)	Pt⁰	70.60	73.87	70.36%
	Pt²⁺	71.25	74.68	29.64%
Pt/C-CeO₂(c)	Pt⁰	71.11	74.44	48.80%
	Pt²⁺	71.69	75.26	51.20%
Pt/C-CeO₂(p)	Pt⁰	71.42	74.83	39.41%
	Pt²⁺	71.91	75.36	60.59%
Pt/C	Pt⁰	71.79	74.93	36.42%
	Pt²⁺	72.64	75.55	63.58%

Table 2

Relative intensity of Ce species in four Pt/C-CeO₂ with different morphologies.
Catalysts	Relative intensity of Ce³⁺	Relative intensity of Ce⁴⁺
Pt/C-CeO₂(s₁)	20.09%	79.91%
Pt/C-CeO₂(s₂)	9.60%	90.40%
Pt/C-CeO₂(c)	32.51%	67.49%
Pt/C-CeO₂(p)	33.22%	66.78%

The electrocatalytic activity of Pt/C-CeO₂ with different morphologies and Pt/C for HER was tested by the LSV in 0.5 M H₂SO₄ solution, and the results are shown in Fig. 5a, which declares that all the catalysts containing CeO₂ have lower over-potential than Pt/C. When the cathode current density is 10 mA cm^− 2, the over-potential of Pt/C-CeO₂(s₂) is approximately 258 mV, which is lower than that of Pt/C-CeO₂(s₁) (265 mV), Pt/C-CeO₂(c) (267 mV), Pt/C-CeO₂(p) (270 mV) and Pt/C (273 mV). The Tafel slopes of Pt/C-CeO₂(s₁), Pt/C-CeO₂(s₂), Pt/C-CeO₂(c), Pt/C-CeO₂(p) and Pt/C are calculated, and the values are 52.9, 42.0, 59.5, 70.7 and 83.3 mV dec^− 1, respectively (Fig. 5b). Undoubtedly, these four catalysts containing CeO₂ all demonstrate remarkable catalytic activity and intrinsic kinetics superior to Pt/C. Moreover, the number of active sites on the catalyst was evaluated through C_dl, which is illustrated in Fig. 5c. Based on the fitting results, Pt/C-CeO₂(s₂) has the highest C_dl value, which is 5.03 mF cm^− 2, indicating that this catalyst possesses the highest number of active sites and the largest electrochemical active surface area. However, the most serious agglomeration of Pt particles in Pt/C-CeO₂(p) (Fig. 3d₄) may be the reason why it has the lowest C_dl value.

Under the same Pt loadings of these catalysts, it is reasonable to attribute the differences in electrocatalytic activity to various CeO₂ morphologies. The excellent catalytic activity of Pt/C-CeO₂(s₂) is mainly ascribed to the following two reasons. Firstly, according to the results of TEM, XRD and the Pt particle size distribution characterization, Pt/C-CeO₂(s₂) possesses the smallest particle size and the better dispersion degree of Pt, which can provide more active sites and electrochemical active surface area. Moreover, the smaller particle size of CeO₂ also has more surfaces to contact with Pt. Secondly, the catalytic activity of Pt for HER is related to the content of Pt⁰. It has been proven that the catalyst with a higher content of the metallic state exhibits superior catalytic performance [42]. Metallic Pt contributes to the high catalytic activity for HER because the 5d orbital of Pt⁰ appears to hybridize with the H 1s orbital to form weak Pt-H valence bonds, leading to a DG (relative free energy) value of approximately zero eV for H* absorption based on the results of density functional theory calculations [43]. As mentioned by XPS analyses, the interaction between Pt and CeO₂ in Pt/C-CeO₂(s₂) is the strongest because the (111) crystal plane is exposed on the surface of small spherical CeO₂ particles, which results in a highest content of Pt⁰. In summary, the catalytic activity order of the four catalysts containing CeO₂ is Pt/C-CeO₂(s₂)> Pt/C-CeO₂(s₁)> Pt/C-CeO₂(c)> Pt/C-CeO₂(p), which is almost positively correlated with the dispersion degree and particle size distribution of Pt and the Pt⁰ content mentioned above.

In addition to catalytic activity, stability is another crucial indicator of the catalyst performance. Figure 6 illustrates the LSV curves of Pt/C-CeO₂(s₂), Pt/C-CeO₂(p) and Pt/C before and after 1000 CV cycles. It is evident that the two LSV curves of Pt/C-CeO₂(s₂) show minimal difference, indicating that this catalyst not only exhibits excellent catalytic activity but also possesses good long-term stability. However, the over-potential of Pt/C-CeO₂(p) changes from 270 mV to 280 mV after 1000 CV cycles when the cathode current density is 10 mA cm^− 2, which suggests a decline in stability. It is worth noting that the stability of both catalysts (Pt/C-CeO₂(s₂) and Pt/C-CeO₂(p)) is superior to that of Pt/C. This finding further emphasizes that the addition of CeO₂ also contributes to the improvement of the catalyst stability to some extent.

The study has successfully demonstrated a promising strategy of utilizing CeO₂ with different morphologies as co-catalysts to enhance the electrocatalytic performance of Pt-based catalysts for the HER process. All four catalysts prepared in this study have exhibited superior performance compared to the Pt/C catalyst. Among the catalysts investigated, the Pt/C catalyst containing spherical CeO₂ with a diameter of 30 ~ 60 nm (Pt/C-CeO₂(s₂)) possesses the best catalytic activity, displaying an over-potential of 258 mV at 10 mA cm^-2 and a Tafel slope of 42 mV dec^-1. Additionally, it also demonstrates outstanding long-term stability, making it a promising candidate for practical applications in the HER. This improvement of catalytic activity is attributed to the small particle size and good dispersion degree of Pt, along with the strong interaction between the exposed (111) crystal plane of small spherical CeO₂ and Pt, which effectively modulates the electron structure of the electrocatalyst. This work not only highlights the significance of controlling the shape and size of CeO₂ to adjust the morphology, electronic structure and thus catalytic performance of the catalysts but also contributes to a deeper understanding for Pt-based catalysts containing metal oxides as co-catalysts towards the HER process.

Ethical Approval

Participants in the study agreed to participate and publish without involving potential conflicts of interest and animal testing.

Competing interests

I declare that the authors have no competing interests as defined by Springer, or other interests that might be perceived to influence the results and/or discussion reported in this paper.

Authors' contributions

All authors contributed to the study conception and design. PR Qi. J You. and Y Wang. wrote the main manuscript text. LL Tian. prepared figures 1 and T Qi. prepared figures 2. All authors reviewed the manuscript.

Funding

The authors are grateful for the financial support by the National Key Research and Development Program of China (2020YFC1909001) and the cooperation project between universities in Chongqing and institutes affiliated to the Chinese Academy of Sciences (Grant No. HZ2021013).

Availability of data and materials

The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

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No competing interests reported.

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Editorial decision: Major revision
16 Aug, 2023
Reviews received at journal
09 Aug, 2023
Reviewers agreed at journal
03 Aug, 2023
Reviewers invited by journal
29 Jul, 2023
Editor assigned by journal
28 Jul, 2023
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You are reading this latest preprint version

Pt/C catalysts containing CeO2 with different morphologies for the hydrogen evolution reaction

Status:

Version 1

Abstract

Figures

Introduction

Experimental

Synthesis of carbon black-supported Pt-CeO₂ with different morphologies

Materials characterization

Electrochemical Measurement

Results and discussion

Conclusions

Declarations

References

Additional Declarations

Status:

Version 1

Pt/C catalysts containing CeO2 with different morphologies for the hydrogen evolution reaction

Status:

Version 1

Abstract

Figures

Introduction

Experimental

Synthesis of carbon black-supported Pt-CeO2 with different morphologies

Materials characterization

Electrochemical Measurement

Results and discussion

Conclusions

Declarations

References

Additional Declarations

Status:

Version 1

Synthesis of carbon black-supported Pt-CeO₂ with different morphologies