Composition-regulated lattice strain of PdSn/C for boosting C1 pathway in ethanol electrooxidation
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Abstract
The rational design of Pd-based catalysts to enhance their applications in ethanol oxidation reaction (EOR) presents both exciting opportunities and significant challenges. Herein, a series of carbon-supported PdSn nanoparticle catalysts (PdSn/C-X, X = 0.1, 0.5, 1, 2) with tunable lattice strains were synthesized using a facile method at room temperature and applied to the EOR. Our findings demonstrate that the activity and stability of EOR can be modulated by manipulating the lattice strain in Pd-based catalysts. Remarkably, PdSn/C-1 exhibits an excellent mass current density of 8,452.3 mA/mgPd, which is higher than that of most Pd-based catalysts, along with great stability, maintaining a mass activity of 573.9 mA/mgPd after 5,000 s. By combining structural analysis, in situ spectral characterization, and theoretical calculation, we elucidate that the optimal tensile strain adjusted by Sn composition in PdSn/C optimizes the free energy of the key intermediate (*CH2CO) during EOR, thereby favoring the C1 pathway and enhancing catalytic activity. This study demonstrates that by controlling the composition, the lattice strain can be altered to improve catalytic performance of Pd-based catalysts in EOR.
Keywords
INTRODUCTION
In recent years, direct ethanol fuel cells (DEFCs) have garnered significant attention due to their non-toxicity, high energy density (8 kWh/kg), and abundant ethanol sources[1-3]. However, the slow reaction kinetics and incomplete oxidation behavior of anodic ethanol oxidation reactions (EOR) hinder the commercialization of DEFCs[4,5]. EOR involves two pathways: complete oxidation (C1 pathway, involving 12 electrons transfer) and partial oxidation (C2 pathway, involving 2 or 4 electrons transfer)[6-10]. The C1 pathway offers a much higher energy density but is impeded by the high energy barrier associated with C-C bond cleavage and the slow desorption of CO-like species during oxidation[11]. Consequently, the C2 pathway predominates in practical applications, leading to poor DEFC efficiency[12]. Thus, developing high-efficiency catalysts that promote the C1 pathway by enhancing C-C bond cleavage and reducing CO poisoning during EOR is crucial for advancing DEFC technology.
To date, Rh- and Ir-based catalysts are known to favor the C2 pathway, but their scarcity, high costs, and low activity and selectivity for EOR limit their commercialization. Alternatively, Pd-based catalysts have shown promising performance due to their excellent catalytic activity[13,14]. However, Pd-based catalysts tend to favor the C2 pathway over the C1 pathway[15,16]. Surface strain engineering on Pd-based catalysts has emerged as an effective method to address this issue by adjusting the d-band properties[17-20], thus regulating the adsorption and desorption of key intermediates and shifting the balance toward the more efficient C1 pathway[8,21,22].
Research indicates that the tensile strain in Pd enhances EOR, while the compressive strain exerts the opposite effect[23]. A common strategy to create tensile strain involves preparing a core-shell structure, such as phosphorus-doped Ag@Pd catalysts, which show 19% selectivity for the C1 pathway due to the tensile strain from the differing lattice constants of Pd and Ag[11]. However, this strategy is limited by a complex multistep preparation process, making it difficult to simply regulate tensile strain. Additionally, Pd active sites are easily poisoned by CO-like intermediates, as they struggle to activate OH species, which are crucial for CO oxidation removal[11]. Previous studies have shown that doping Pd-based catalysts with oxyphilic metals enhances the removal of CO-like intermediates by facilitating the generation of OH species[24,25]. Thus, introducing oxyphilic atoms into Pd catalysts to regulate tensile strain and remove CO-like intermediates is a promising but underexplored approach.
Herein, we present our research on lattice strain-regulated activity of carbon-supported PdSn nanoparticles (NPs) catalysts for EOR, using a simple wet chemical method[26]. By adjusting the Sn content in PdSn NPs, we achieved various lattice strains in PdSn/C. PdSn/C-1, with an optimal tensile strain of 3.7%, demonstrated remarkable catalytic activity and enhanced stability compared to other Pd-based catalysts. The incorporation of oxyphilic Sn provides effective sites for the removal of CO-like species, improving the tolerance to CO-like intermediates. In situ attenuated total reflectance surface-enhanced infrared spectroscopy (ATR-SEIRAS) and density functional theory (DFT) calculations revealed that appropriate tensile strain in PdSn NPs significantly improves electrocatalytic activity by tuning the adsorption properties of key reaction intermediates (*CH2CO) for further C-C bond cleavage. Our work introduces a novel strategy to modulate tensile strain in Pd-based catalysts for EOR through composition regulation and offers a comprehensive mechanism for EOR enhancement.
EXPERIMENTAL
Materials and reagents
Palladium chloride (PdCl2) was obtained from Energy Chemistry. Stannous chloride (SnCl2, 99.9%). Sodium citrate (Na3C6H5O7·2H2O, 99.9%), ethanol (CH3CH2OH, 99.7%), sodium borohydride (NaBH4, 99.9%), and potassium hydroxide (KOH) were provided by Shanghai Sinopharm Chemical Reagent Co., Ltd. Activated carbon (Vulcan XC-72) was sourced from Shanghai Macklin Biochemical Co., Ltd. Nafion solution (5 wt% in propanol and water) was purchased from Alfa Aesar. All reagents were of analytical grade and used without further purification. H2O (18 MΩ) was purified using an ultra-pure purification system (HHitech, Eco-S15UF).
Preparation of PdSn/C catalysts
PdCl2 (88 mg) was dissolved in 4.4 mL of water under magnetic stirring. Three drops of hydrochloric acid were added to adjust the acidity, and the mixture was left to stand for 2 h until complete dissolution was achieved. Then, 0.0948 g (0.5 mmol) of SnCl2 and 2.358 g (8 mmol) of sodium citrate were added. Sodium citrate was used as a complexing agent to coordinate with Pd and Sn ions for uniform dispersion. The solution was diluted with 200 mL of water, followed by the addition of 200 mg of XC-72 with sonication for 30 min. Next, 50 mL of 0.1 M NaBH4 was used as a reductant and injected into the mixture, followed by vigorous stirring at 25 °C for 8 h. The resulting suspension was centrifuged at 10,000 rpm for 5 min, and the supernatant was discarded. The sediment was washed with water and centrifuged three times. The collected product was dried in a vacuum oven at 60 °C for 5 h, resulting in the formation of PdSn/C-1. By varying the amounts of SnCl2 (0.0316, 0.0474, and 0.1896 g), different PdSn/C catalysts were obtained, labeled as PdSn/C-0.1, 0.5, and 2, respectively. Additionally, as a control material, Pd/C was synthesized using the same procedure without adding SnCl2.
Materials characterizations
Transmission electron microscopy (TEM, JEM-F200) and energy-dispersive X-ray spectroscopy (EDS, FEI Talos F200X) were employed to determine the morphology and chemical composition of the materials.
Electrochemical measurements
Electrochemical measurements were conducted using a three-electrode setup with an electrochemical workstation (AMETEK PARSTAT 4000A, Princeton). A glassy carbon electrode (GCE) with an internal area of 0.07068 cm2 served as the working electrode. Platinum foil (2 cm × 2 cm) and saturated calomel electrode (SCE) were used as the counter and reference electrodes, respectively. All experiments were conducted at room temperature, and all applied potentials were referenced to the reversible hydrogen electrode (RHE) based on Nernst equation
Electrochemical measurements were conducted between 0.27 and 1.47 V at a scan rate of 50 mV/s in N2-saturated 1.0 M KOH or 1.0 M KOH + 1.0 M ethanol electrolyte. The electrochemically active surface area (ECSA) was calculated from the cyclic voltammetry (CV) curves in the PdO reduction peak region using
In situ ATR-SEIRAS characterization
A three-electrode cell was employed for all SEIRAS tests, with a GCE, Ag/AgCl, and carbon rod as the working, reference, and counter electrodes, respectively. EOR measurements were conducted in an electrolyte of 1.0 M KOH + 1.0 M ethanol under N2-saturated solution. The background spectrum was collected at 0.5 V while the potential was swept from 0 to 1.3 V.
Theoretical calculation methods
The DFT calculations were performed using the Vienna Ab Initio Simulation Package (VASP 6.3.0)[27]. The Perdew-Burke-Ernzerhof (PBE) functional was employed within the generalized gradient approximation (GGA) framework to compute the electronic exchange-correlation energy[28]. The projector augmented wave (PAW) method was used to describe the ion-electron interactions[29]. The structure was fully optimized using a conjugate gradient optimization technique, with a cutoff energy of 450 eV for the plane-wave basis set. A 3 × 3 × 1 Monkhorst-Pack grid was employed during structural optimization. The maximal force on each atom was set to be less than 0.02 eV/Å, with an energy change convergence criterion of less than 1 × 10-5 eV. The DFT-D3 semi-empirical correction was applied using Grimme's scheme. The Gibbs free energy change (ΔG) was defined for each elementary step as ΔG = ΔE + ΔZPE - TΔS, where ΔE is the adsorption energy from DFT calculations, ΔZPE is the zero-point energy correction, T is the temperature, and ΔS is the entropy change.
RESULTS AND DISCUSSION
Material synthesis and characterization
We synthesized a series of PdSn NPs supported on activated carbon, labeled as PdSn/C-X (X = 0.1, 0.5, 1, 2, representing the Sn/Pd molar ratio in the precursor), using a straightforward co-reduction process at room temperature [Figure 1A]. TEM images [Figure 1B-F] reveal that the PdSn NPs (indicated by the white dotted circles) are uniformly distributed on the carbon support without aggregation. Additionally, statistical analysis of 100 well-distributed Pd and PdSn NPs indicates an average particle size ranging from 3.0 to
Figure 1. (A) Schematic illustration of preparing PdSn/C-X. TEM images of (B) Pd/C, (C) PdSn/C-0.1, (D) PdSn/C-0.5, (E) PdSn/C-1, and (F) PdSn/C-2.
To gain further insight into the surface structure of PdSn/C-X, we employed aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and XRD. HAADF-STEM images at the atomic level [Figure 2A] show the lattice spacing of PdSn NPs, which were measured from the cyan line region covering ten planes. The lattice distances of the Pd/C and PdSn/C-0.1, 0.5, 1, and 2 catalysts were measured to be 2.16, 2.17, 2.19, 2.24, and 2.28 Å, respectively, corresponding to the (111) lattice plane of Pd[24]. Additionally, a lattice spacing of 2.91 Å was observed in PdSn/C-2, indicating the presence of the PdSn (111) phase in this sample[30]. It is worth emphasizing that the observed increase in the interplanar spacing indicates the presence of tensile strain resulting from the incorporation of Sn (which has a larger parameter compared to Pd) into the Pd lattice[31], as will be further supported by the XRD investigation. Furthermore, we defined the tensile strain as (dp-ds)/ds, where the dp represents the interplanar spacing of the doped sample, and ds indicates the interplanar spacing of the pure reference sample[32]. We therefore approximated the tensile strains of 0.46%, 1.39%, 3.7%, and 5.6% for the surfaces of
Figure 2. (A) HAADF-STEM images, (B) Lattice stretching ratios, and (C) XRD patterns of Pd/C and PdSn/C-X. (D) XRD profiles and Rietveld refinement fit for PdSn/C-1.
Recent studies suggest that the highest occupied electronic states up to the Fermi level serve as electronic descriptors for electrocatalytic activity[41], as they influence the adsorption and desorption characteristics of reactants and intermediates. Therefore, we conducted density of states (DOS) simulations for the active Pd center using DFT (see Supplementary Material) to understand how strained structures affect surface adsorption behavior [Supplementary Figure 3A]. The Pd d-band center shows a strong correlation with tensile strain [Supplementary Figure 3B], and its value decreases toward the Fermi level as tensile strain increases. According to the d-band theory of metal-adsorbate interactions, this change in d-band electron density has significant catalytic implications[42]. A higher local average of the d-band electron energies (ɛd) near the Fermi level results in a stronger binding strength between the active site and adsorbates[43]. However, if ɛd is too low, the reactants struggle to adsorb, while a high ɛd causes strong adsorption of intermediates, leading to catalyst poisoning[44]. Therefore, an optimal ɛd level accelerates the absorption of reaction intermediates at the active site and promotes the subsequent oxidation phase during the EOR, thereby enhancing catalytic performance.
The surface chemical compositions of PdSn/C catalysts were further analyzed by XPS, using the C1s peak at 284.8 eV for calibration. The survey spectra [Supplementary Figure 4A] confirm the presence of Pd, Sn, and C. High-resolution spectra of Pd 3d for PdSn/C-0.1 to 2 [Supplementary Figure 4B] were deconvoluted into four peaks around 335.9, 337.4, 341.7, and 344.9 eV, corresponding to Pd(0)3d5/2, Pd(II)3d5/2, Pd(0)3d3/2, and Pd(II)3d3/2[11], respectively. The high-resolution spectra of Sn 3d [Supplementary Figure 4C] show four peaks around 485.6, 493.9, 487.5, and 495.8 eV, corresponding to Sn(0)3d5/2 Sn(IV)3d5/2, Sn(0)3d3/2, and Sn(IV)3d3/2, respectively. Notably, the Pd(0)3d5/2 peak shifts to lower binding energy with increasing Sn content, indicating significant electron transfer to Pd. In addition, the proportions of Pd(0) for PdSn/C-0.1, 0.5, 1, and 2 were calculated to be 67.3%, 43.1%, 40.9%, and 46.3%, respectively, based on the peak areas of Pd(0) in Supplementary Figure 4B. The higher proportions of Pd(0) at high Sn content (PdSn/C-2) owes to SnO2 formation, which hinders Pd oxidation and increases the Pd(0) proportion, demonstrating that Sn incorporation influences Pd valence states due to its oxyphilic properties[31]. Supplementary Figure 4D shows the high-resolution spectra of the O1s region on PdSn/C. The fitted peaks at 532.2, 533.7, and
Catalytic performance of PdSn/C for EOR
The electrocatalytic performance of the as-prepared PdSn/C catalysts was thoroughly evaluated. Before EOR testing, the CV curves of PdSn/C and Pd/C catalysts were recorded in a N2-saturated 1.0 M KOH solution [Figure 3A]. The observed cathodic peak around 0.7 V during the backward scans is attributed to the reduction of the Pd oxide layer. Notably, the cathodic peaks of PdSn/C-0.1, 0.5, 1, and 2 are at 0.70, 0.69, 0.71, and 0.73 V (inset in Figure 3A), indicating a more positive peak potential compared to Pd/C (0.68 V). This shift implies the desorption of oxygenated species from their surfaces[15]. Based on the reduction peak area and the Pd content on the working electrode, the ECSAs of PdSn/C-0.1, 0.5, 1, 2, and Pd/C were calculated to be 38.6, 48.5, 104.3, 72.3, and 4.0 m2/gPd [Supplementary Figure 5A], respectively. The ECSA of PdSn/C initially grows and then decreases as the Sn content increases. The initial increase is attributed to the enhanced lattice expansion in PdSn/C-0.1 to 1, which activates additional Pd sites. However, the presence of the intermetallic PdSn phase reduces the number of active Pd sites[31]. The electrocatalytic activities of these catalysts for EOR were assessed through CVs recorded in 1.0 M KOH + 1.0 M ethanol solution. Figure 3B shows two typical oxidation peaks in the forward and backward scans, representing the oxidation of ethanol and carbonaceous intermediates, respectively. As shown in Figure 3C, to compare the activities, mass and specific activities were determined by normalizing the peak current densities of ethanol oxidation to the mass of Pd and the ECSAs, respectively. PdSn/C-1 exhibits significantly higher activity (8,452.3 mA/mgPd or 8.1 mA/cm2) than PdSn/C-0.1 (2,212.6 mA/mgPd or 3.7 mA/cm2), PdSn/C-0.5
Figure 3. CV curves of Pd/C and PdSn/C-X in (A) 1.0 M KOH solution (inset: the magnified view of reduction peaks) and (B) 1.0 M KOH with 1.0 M ethanol solution. (C) Summarized mass activities (left) and specific activities (right) of Pd/C and PdSn/C-X. (D) i-t measurements at -0.24 V of Pd/C and PdSn/C-X in 1.0 M KOH + 1.0 M ethanol solution.
Furthermore, the catalytic kinetics were investigated using linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) techniques. As shown in Supplementary Figure 5B, PdSn/
Finally, electrochemical CO stripping tests were performed on the PdSn/C catalysts to evaluate their capability for removing carbonaceous intermediates. CO stripping voltammograms were obtained by applying a voltage of 0.27 V to the working electrode for 20 min in a CO-saturated 1.0 M KOH electrolyte solution. As shown in Supplementary Figure 8, peaks at 0.88 and 1.08 V in all curves correspond to CO stripping, involving the oxidation of adsorbed CO and its intermediates according to the literature[48-50]. CO adsorbed on the catalysts was nearly completely removed after one scan between 0.27 and 1.47 V. The onset potentials of CO stripping for PdSn/C-0.1, 0.5, 1, and 2 (marked in Supplementary Figure 8) are downshifted by 0.12, 0.15, 0.23, 0.20 V, respectively, from that of Pd/C (at 0.78 V), indicating a reduced tendency for CO poisoning. In addition, among the catalysts with varying Pd/Sn ratios, the PdSn/C-1 catalyst exhibits the largest CO oxidation/removal peak area and the most negative onset potential for CO stripping, suggesting easy CO removal and an effective enhancement of CO tolerance with Sn incorporation[24,25,51]. Notably, appropriately doped Sn, as seen in PdSn/C-1, demonstrates superior CO tolerance, thereby enhancing the catalyst's performance.
Mechanistic investigation of PdSn/C-1 for EOR
To gain insights into how the metal composition of the catalysts affects reaction pathway selectivity during EOR, we conducted in situ ATR-SEIRAS studies using PdSn/C-1 and Pd/C catalysts in 1.0 M KOH solution containing 1.0 M ethanol. The spectra obtained during the positive potential sweep for the Pd/C catalyst are shown in Figure 4A. The appearance of the CO band at 1,800 cm-1 within the voltage range of 0 to 1.3 V indicates that the catalyst is capable of undergoing C-C bond cleavage, resulting in the predominance of bridge CO adsorption on the Pd sites[52-54]. This suggests the presence of intermediates via the C1 pathway[55]; however, the adsorbed CO may lead to significant poisoning, hindering the catalytic process. Thus, the C2 pathway dominates during catalytic processes on the Pd/C catalyst, as evidenced by the peaks around 1,420 cm-1, which are assigned to the stretching vibration of CH3COO-[56].
Figure 4. In situ ATR-SEIRAS spectra of (A) Pd/C and (B) PdSn/C-1 in N2-saturated 1 M KOH + 1 M C2H5OH solution.
However, the PdSn/C-1 catalyst exhibits no adsorbed CO on its surface [Figure 4B] due to the Sn introduction. Notably, a distinct CO2 adsorption peak emerges, and its intensity increases with potential. Peaks around 2,980 cm-1, assigned to the vibrational characteristics of C-Hx fragments from the methoxy group of ethanol remaining on the catalyst surface after C-C bond cleavage[57], are observed on PdSn/C-1 (right in Figure 4B) but not on the Pd/C catalyst (right in Figure 4A). These results indicate that ethanol electrooxidation on PdSn/C-1 primarily yields CO2 through the C1 pathway via C-C bond cleavage. Additionally, the strong vibration of H2O at 1,620 cm-1 on PdSn/C-1 (absent on Pd/C) implies the production of abundant OH- species on oxyphilic Sn for the oxidation removal of *CO[31,58], resulting in significant catalytic activity. Furthermore, a weak peak around 1,400 cm-1 was observed in Figure 4B, which can be deconvoluted into two peaks at 1,402 and 1,394 cm-1 [Supplementary Figure 9A] attributed to acetate and carbonate[55], respectively. Thus, despite the limitation of intensity, the C1 selectivity (η, in %) was approximately quantified using η = Ccarbonate/(Ccarbonate + Cacetate) = 6A1394/(6A1394 + 4A1402 × 2.2) × 100%[31], where A1394 and A1402 are the peak areas at 1,394 and 1,402 cm-1, 6 and 4 refer to the number of electrons transferred per one of carbonate and acetate, respectively, and 2.2 is the ratio of the absorbance coefficient per mole of carbonate and acetate. As shown in Supplementary Figure 9B, the η of PdSn/C-1 reached approximately 35.1%, indicating a significant C-C cleavage ability. In summary, the C1 pathway involves the dissociation and adsorption of ethanol, leading to the splitting of the C-C bond and generating hydrogen-rich C1 fragments that undergo complete oxidation without forming toxic intermediates[52].
The EOR mechanism is complex, generally involving C1 and C2 reaction pathways with various surface intermediates[59,60]. To elucidate the reaction mechanism of EOR, we conducted DFT simulations to evaluate the adsorption energy of the Pd (111) surface (as considered according to the XRD results) toward the intermediates during EOR [Supplementary Figure 10]. The free energy profiles of EOR leading to C2
Figure 5. (A) Potential energy diagram for EOR via the C1 (green) and C2 (yellow) pathway on Pd (111). (B) The calculated free energy for ΔG1 and ΔG2 on various tensile ratios of Pd (111). (C) Schematic illustration for the EOR process on Pd/C (left) and PdSn/C-1 (right).
Structural analysis, electrochemical evolution, in situ ATR-SEIRAS studies, and DFT calculations collectively demonstrate that the incorporation of Sn into the Pd catalyst enhances the catalytic performance for EOR through two pivotal processes [Figure 5C]. First, Sn doping regulates the tensile strain of the Pd crystal, reducing the energy barrier between *CH3CO and *CH2CO (ΔG2) and promoting the C1 pathway. Notably, the optimal ΔG2 for improved selectivity and kinetics is achieved only with suitable tensile strain (PdSn/C-1). Second, and importantly, the incorporation of Sn provides the oxyphilic sites for OHads species, facilitating the oxidation removal of CO for enhanced anti-poisoning. These dual contributions underlie the exceptional catalytic performance of PdSn/C-1 in EOR.
CONCLUSIONS
In conclusion, we have developed an efficient co-reduction approach to synthesize PdSn/C catalysts, enabling tunable tensile strain through modulation of Sn content. The PdSn/C-1 catalyst has demonstrated superior catalytic efficacy in EOR, achieving a mass activity of 8,452.3 mA/mgPd, surpassing that of most Pd-based catalysts. Additionally, Sn incorporation has enhanced the tolerance to COads species through oxidation removal. By combining the results of ATR-SEIRAS and DFT calculations, we found that the appropriate Sn component in PdSn/C creates an optimal tensile strain. This strain lowers the reaction energy barrier for the formation of *CH2CO from *CH3CO intermediates, a key step in EOR, and favors the C1 pathway through C-C bond cleavage. The strategy of component-regulated strains to enhance catalytic performance in EOR holds promise for the future design of advanced electrocatalysts.
DECLARATIONS
Authors’ contributions
Prepared the PdSn/C and performed most of the electrochemical experiments: Tao, Y.
Prepared the PdSn/C and physicochemical characterizations: Cai, Y.
Conducted ATR-SEIRAS experiments: Ding, J.
Performed theoretical calculations: Li, F.
Analyzed the data and wrote and discussed the whole paper: Ma, T.
Supervised students, developed concepts, acquired funding, and revised the manuscript: Chen, R.; Ma, T.; Liang, F.
Availability of data and materials
The data are available upon request from the authors.
Financial support and sponsorship
This work was financially supported by the National Natural Science Foundation of China (Nos. 21871108, U21A20317) and the Program for Innovative Teams of Outstanding Young and Middle-Aged Researchers in the Higher Education Institutions of Hubei Province (No. T201702).
Conflicts of interest
All authors declared that there are no conflicts of interest.
Ethical approval and consent to participate
Not applicable.
Consent for publication
Not applicable.
Copyright
© The Author(s) 2025.
Supplementary Materials
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Cai, Y.; Tao, Y.; Ding, J.; Li, F.; Chen, R.; Ma, T.; Liang, F. Composition-regulated lattice strain of PdSn/C for boosting C1 pathway in ethanol electrooxidation. Energy Mater. 2025, 5, 500038. http://dx.doi.org/10.20517/energymater.2024.91
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