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Article

Enhancing Propane Dehydrogenation Performance on Cerium-Modified PtSnIn/Al Trimetallic Catalysts

by
Jinbao Liu
,
Ke Xia
and
Fen Zhang
*
School of Food & Tourism, Shanghai Urban Construction Vocational College, Shanghai 201415, China
*
Author to whom correspondence should be addressed.
Catalysts 2025, 15(5), 506; https://doi.org/10.3390/catal15050506
Submission received: 12 April 2025 / Revised: 18 May 2025 / Accepted: 19 May 2025 / Published: 21 May 2025
(This article belongs to the Special Issue Catalytic Removal of Volatile Organic Compounds (VOCs))
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Abstract

:
The effects of Ce incorporation into trimetallic PtSnIn-supported catalysts were investigated for a propane dehydrogenation reaction with advanced characterization techniques. It was found that some Ce species exist in the form of CeAlO3 on the reduced PtSnIn/xCe-Al catalyst, significantly enhancing the thermal stability of the alumina support. The NH3-TPD measurements verified that the total acidity of the PtSnIn/xCe-Al catalysts decreases with the addition of Ce. The PtSnIn/1.5Ce-Al catalyst exhibits the optimal particle distribution with the smallest Pt particle size of 8.0 nm, which was revealed by TEM. The H2-TPR and XPS results suggest that more oxidized-state Sn species form on catalyst surfaces, and the metal–support interaction can be strengthened when Ce is introduced. Furthermore, TG analysis demonstrates that Ce incorporation substantially reduces coke formation on the spent catalysts. The PtSnIn/1.5Ce-Al catalyst exhibits exceptional catalytic performance, achieving an initial propane conversion of 62.6% and maintaining a conversion of 57.2% after a 120 min reaction. In addition, the PtSnIn/1.5Ce-Al catalyst possesses high long-term stability. Over 40.0% propane conversion can be maintained after a 53 h continuous PDH reaction. These findings highlight the pivotal role of Ce in improving the structural properties and catalytic performance of PtSnIn-based catalysts for propane dehydrogenation, offering valuable insights for the design of highly efficient and stable dehydrogenation catalysts.

1. Introduction

Propylene is a crucial feedstock in the petrochemical industry, widely used for the production of polypropylene, acrylonitrile, acrylic acid, and other valuable chemicals [1,2,3]. With the increasing global demand for propylene, propane dehydrogenation (PDH) has emerged as a promising and economically viable route for propylene production, especially in light of the abundant availability of propane from shale gas resources [4]. The PDH process offers high selectivity to propylene and aligns with the growing need for on-purpose propylene production technologies [5,6].
Pt-based catalysts have been extensively studied for PDH due to their high intrinsic activity and environmentally friendly properties [7,8,9]. However, the industrial application of Pt-based catalysts faces significant challenges, including rapid deactivation caused by coke deposition and sintering of Pt particles under the high-temperature conditions required for the endothermic dehydrogenation reaction [10,11]. To address these issues, the introduction of secondary and tertiary metals, such as Sn and In, has been widely explored. These additives not only improve the dispersion of Pt but also modify its electronic properties, thereby enhancing catalytic performance and stability [12,13,14,15]. Among these, bimetallic Pt-Sn catalysts have demonstrated remarkable activity and selectivity in PDH, but further improvements are necessary to achieve higher propylene yields and longer catalyst lifetimes [16,17,18].
Alumina (γ-Al2O3) is the most common support for Pt-based PDH catalysts due to its favorable textural properties, thermal stability, and ability to maintain high Pt dispersion [19,20,21]. However, the strong acidity of alumina often leads to undesirable side reactions, such as cracking and coking, which reduce propylene selectivity and catalyst stability [13,21,22]. To mitigate these issues, the incorporation of metal species into the alumina framework has been proposed to neutralize surface acidity and enhance metal–support interactions [23,24,25]. Rare earth metals, such as cerium (Ce), lanthanum (La), and yttrium (Y), have shown significant promotional effects in improving the thermal stability of alumina supports and strengthening the interaction between active metals and the support [24,26,27,28]. In particular, CeO2 has been widely recognized for its unique oxygen storage capacity and redox properties, which can effectively suppress coke formation and stabilize Pt particles during the dehydrogenation process [15,27,29]. For instance, Kwon et al. [30] reported that Ce-doped γ-Al2O3 can generate atomically dispersed Ce3+ sites, which leads to a strong metal–support interaction (SMSI) to suppress the sintering of Pt0 species. Naseri et al. [31] found that Ce-modified PtSn/γ-Al2O3 catalysts exhibit high catalytic performance and enhanced thermal stability. Wang et al. [15] reported that introducing the proper amount of Ce modulates the electronic interaction between Pt, In, and the carrier, simultaneously acting as an effective physical barrier to prevent the aggregation of the isolated active species. The published studies on propane dehydrogenation catalysts only reported the effect of Ce introduction on the structure and propane dehydrogenation performance of Pt-based monometallic catalysts and PtSn or PtIn bimetallic catalysts, but the introduction of Ce additives into more complicated PtSnIn ternary catalyst systems has never been reported.
The aim of our work is to investigate the promotional effects of Ce on trimetallic PtSnIn/Al catalysts for propane dehydrogenation. A series of PtSnIn/xCe-Al catalysts with varying Ce loadings were prepared using a sequential impregnation method. For comparison, monometallic Pt/Al and bimetallic PtSn/Al catalysts were also synthesized. The catalytic performance of these materials was evaluated in terms of propane conversion, propylene selectivity, and stability under industrially relevant conditions. Advanced characterization techniques, including BET, XRD, NH3-TPD, H2-TPR, XPS, TEM, and TG, were employed to elucidate the structure–performance relationships and the role of Ce in enhancing the catalytic properties. The findings of this study are expected to provide valuable insights into the design of highly efficient and stable Pt-based catalysts for propane dehydrogenation.

2. Results and Discussion

2.1. Characterizations of PtSnIn/xCe-Al Catalysts

Table 1 gives the textural properties of the PtSnIn/xCe-Al catalysts after reduction at 580 °C for 2.5 h. It can be seen that the specific surface area (SBET) of the alumina carrier is higher than that of the promoted catalysts, suggesting that some metal species entered into the channels of γ-Al2O3. The SBET shows a trend to increase with the increase in Ce content (≤1.5 wt.%). However, a smaller SBET is found in the PtSnIn/2.5Ce-Al catalyst. The variation in the SBET could be related to the influence of CeO2 on the thermal stability of alumina. Damyanova et al. [32] also reported that that CeO2 could stabilize γ-Al2O3 against surface area loss, which depends on CeO2 loading. Low CeO2 loading is the most effective in promoting the thermal stability of alumina while high CeO2 loading is almost ineffective [29].
Figure 1 presents the XRD patterns of the PtSnIn/xCe-Al catalysts after reduction at 580 °C for 2.5 h. As can be observed, no catalysts show any diffraction peaks of Pt, Sn, or In species, which is ascribed to their small particle size and/or low concentration below the XRD detection limit [33]. The representative peaks at ~37.5°, ~45.8°, and ~66.9° can be noted over all the samples, which are assigned to the γ-Al2O3 phase [34]. The similar XRD patterns indicate that the original γ-Al2O3 structure is well preserved during the catalyst preparation process. However, for PtSnIn/2.5Ce-Al catalysts, it must be noted that slight diffraction lines of CeO2 fluorite structure appeared at 2θ = 28.5° [32]. The characteristic peaks of Ce-related crystalline phases are not clear for catalysts with Ce loading <2.5 wt.% due to the low concentration of cerium or the small crystallite size below the XRD detection limit [29]. Riguetto et al. [35], using the XPS method, found that some Ce species could exist in the form of CeAlO3 on a reduced Pt-CeO2/Al2O3 catalyst with low Ce loading.
The above BET and XRD techniques prove that the presence of Ce can promote the thermal stability of alumina against the loss of SBET of PtSnIn/xCe-Al catalysts. This behavior may be related to the formation of Ce3+ as CeAlO3 under a reducing atmosphere, which prevents the surface diffusion of catalyst species from sintering [29]. According to a model proposed by Piras et al. [36], the geometrical arrangement between CeAlO3 and CeO2 favors the formation of microdomains that act as barriers for surface diffusion. Shyu et al. [37] have also found that the strong interaction between dispersed Ce and alumina of Pt/Ce-Al2O3 results in the formation of surface CeAlO3 by Ce3+ occupying vacant octahedral sites on the alumina surface. This initial occupation of octahedral sites by Ce3+ blocks the transition of Al3+ from tetrahedral to octahedral sites during high-temperature treatment, which causes the loss of the surface area of alumina [32]. The high catalytic activity of the PtSnIn/xCe-Al catalyst at elevated temperatures may partly result from the improvement in the thermal stability of alumina.
The dehydrogenation performance of propane is greatly dependent on the acidity of the catalyst [6]. The acidity of the different catalysts was examined by the NH3-TPD method, and the corresponding NH3-TPD profiles are depicted in Figure 2. It is clear that the NH3 uptake curves of different samples were deconvoluted into three fitted peaks using the Gaussian function. The semi-quantitative results of the acidity strength distribution are summarized in Table 2. The low-temperature peaks (peak I at 170–200 °C and peak II at 250–320 °C) can be ascribed to weak and medium-strength acid sites, whereas the peak (peak III) above 250 °C is typical of strong-acidity sites [33]. Compared with the bare support, a distinct decrease in the strong acid sites and the total acidity can be observed over PtSnIn/0.0Ce-A. The addition of Ce leads to a further decrease in the total amount of acidity but an increase in the fraction of the strong acid sites, which indicates that the effect of Ce species on the support acidity is not the main reason for the improving catalytic performance. Similar results have been reported by Yu et al. [29] and Xue et al. [38].
As displayed in Figure 3, the PtSnIn/0.0Ce-Al sample exhibits three reduction peaks: peak I at ~340 °C, peak II at ~505 °C, and peak III at ~770 °C. Peak I can be easily linked to the reduction of Pt oxide species, and peak II can be assigned to the reduction of Pt species interacting strongly with carrier and/or the co-reduction of PtSnIn [13,39]. When Ce is introduced, two new peaks can be observed over PtSnIn/0.5Ce-Al: one at ~120 °C and the other at ~637 °C. The peak at the lower temperature shifts to a higher temperature of 196 °C as the Ce addition increases up to 2.5 wt.%. This phenomenon can be explained by the highly dispersed Pt species being reduced and then located on the external surface of the support [40]. Nevertheless, the peak intensity at ~637 °C gradually becomes wider and shifts to lower temperatures of 565 °C and 530 °C for the PtSnIn/1.5Ce-Al and PtSnIn/2.5Ce-Al catalysts, respectively. According to the literature [41], this finding may be caused by the formation of a nonstoichiometric oxide, CeO2−x or CeAlO3, which becomes thermodynamically possible at this temperature. Based on these results, it can be concluded that the addition of Ce can affect the reducibility of catalysts to different degrees.
The XPS spectra of Sn3d5/2 and In3d5/2 of the PtSnIn/0.0Ce-Al and PtSnIn/1.5Ce-Al catalysts are shown in Figure 4 and Figure 5, respectively. The semi-quantitative results are listed in Table 3. As displayed in Figure 4, three fitting peaks can be obtained by the deconvolution method. The peak at a low binding energy (~485.5 eV) is ascribed to zerovalent Sn, while the other two peaks at higher binding energies (~486.7 and ~487.5) can be associated with different oxidation states of Sn (Sn2+ and Sn4+) [42,43,44]. It has been proposed that the close binding energies of Sn2+ and Sn4+ make distinguishing between them difficult [45]. For comparison, in Table 3, it is obvious that the percentage of Sn0 (14%) of PtSnIn/1.5Ce-Al is lower than that (26%) of the PtSnIn/0.0Ce-Al catalyst, suggesting that larger numbers of oxidized-state Sn species exist on the surface of the PtSnIn/1.5Ce-Al catalyst. It can be explained that Ce addition inhibits the reduction of Sn species.
Figure 5 shows the XPS spectra of In3d5/2 of the reduced PtSnIn/0.0Ce-Al and PtSnIn/1.5Ce-Al catalysts. Both catalysts present two peaks in the In3d5/2 XPS spectra at ~444.2 eV and ~445.2 eV, belonging to the zerovalent In (In0) or or the PtIn alloy phase and the oxidation state of the In species, respectively [13]. It is worth noting from Table 3 that the addition of Ce to the PtSnIn/Al catalyst contributes to a negligible change in the ratio of In0 and In3+ (~3:7), implying that the presence of Ce has no influence on the reducibility of In species.
The XPS spectra of Ce3d of the reduced PtSnIn/1.5Ce-Al catalyst are displayed in Figure 6. The complex spectrum of Ce-related species can be resolved into eight components by least-squares fitting with the assignment as defined by Shyu et al. [46] and Park et al. [47] (v’s represent the Ce 3d5/2 contribution and u’s represent the Ce 3d3/2 contribution). It can be seen that the relative intensity of v’/v and u’/u substantially increases, indicating that CeA1O3 exists in the reduced PtSnIn/1.5Ce-Al catalysts [46]. The result is in good agreement with the XRD analysis.
The TEM images and corresponding Pt particle size distribution of the reduced PtSnIn/xCe-Al catalysts are illustrated in Figure 7. The Pt particle sizes of the PtSnIn/0.0Ce-Al, PtSnIn/1.5Ce-Al, and PtSnIn/2.5Ce-Al catalysts were calculated statistically to be 10.8, 8.0, and 11.3 nm (listed in Table 1), respectively. Obviously, the average Pt particle size of PtSnIn/1.5Ce-Al is the smallest among these samples, simultaneously accompanied by the best distribution, depicted in Figure 7, implying that the appropriate amount of Ce in PtSnIn/xCe-Al catalysts could promote formation of small and highly dispersed Pt particles. This result may be attributed to the formation of a Pt–O–Ce bond, which acts as an anchor to inhibit Pt migration [48]. In contrast to this, it should be observed that Pt particles tend to agglomerate on the surface of the PtSnIn/2.5Ce-Al catalyst. This phenomenon is easily associated with the fact that excessive Ce content may cover and block the active sites on the catalyst’s surface [49].

2.2. Catalytic Performances

The catalytic performances of the catalysts with different metallic compositions in propane dehydrogenation are depicted in Figure 8. For comparison, the catalytic performances of Pt/Al and PtSn/Al are also illustrated in parallel. The initial conversions of propane catalyzed by Pt/Al, PtSn/Al, PtSnIn/Al, and PtSnIn/1.5Ce-Al catalysts are 29.5%, 37.5%, 58.4%, and 62.6%, respectively. After reacting for 120 min, the conversions decrease to 16.0%, 24.7%, 51.5%, and 57.2%, respectively. It is clearly observed that the monometal Pt/Al catalyst displays the lowest conversion and selectivity. Addition of both Sn and In to the Pt/Al catalyst leads to the enhancement of catalytic activity. The highest initial catalytic conversion (62.6%) and the most stable propylene selectivity above 96.0% are obtained with the PtSnIn/1.5Ce-Al catalyst.
Figure 9 displays the propane conversion and propylene selectivity over the PtSnIn/xCe-Al catalysts in terms of Ce content. The initial propane conversion of the PtSnIn/0.0Ce-Al catalyst drops from 58.4% to 51.5% after a 120 min reaction. When the Ce loading is in the range of 0.6–1.5 wt.%, the catalytic activity and stability are evidently improved. The maximum initial and final propane conversions (62.6% and 57.2%) can be obtained for the PtSnIn/1.5Ce-Al catalyst. However, the propane conversion evidently declines as Ce loading further increases to above 1.5 wt.%. It is possible that higher Ce loading changes the support structure and properties.
To verify the regenerability of the catalysts, a PtSnIn/1.5Ce-Al sample was selected for the reaction–regeneration test with four cycles. The spent catalyst was regenerated under an air atmosphere (a flow rate of 30 mL/min) in situ at 550 °C for 2 h. After regeneration, the catalyst was activated in H2 at 580 °C for 2.5 h prior to the next reaction. As shown in Figure 10, the PtSnIn/1.5Ce-Al catalyst exhibits stable catalytic performance over four successive propane dehydrogenation reaction–regeneration cycles. The initial propane conversion still attains over 60.0%, with only a slight decline of ~2% after four reaction–regeneration cycles. Meanwhile, the propylene selectivity is maintained at an excellent level of around 96% throughout the four cycles, showing negligible degradation during the reaction process. These results demonstrate that the PtSnIn/1.5Ce-Al catalyst retains its catalytic activity effectively after regeneration, confirming its robust recyclability.
Figure 11 shows the catalytic stability of the PtSnIn/1.5Ce-Al catalyst for the propane dehydrogenation reaction. As can be seen, the propane conversion is maintained above 40.0% after a 53 h PDH reaction. The propylene selectivity is maintained above 96.0% for 50 h. The results demonstrate that excellent catalytic properties of the PtSnIn/1.5Ce-Al catalyst are obtained in this work. A comparison between the best catalyst of the present study and some other Pt-based catalysts in the literature is summarized in Table 4. It can be found that the PtSnIn/1.5Ce-Al catalyst presented in this study is very competitive in terms of both catalytic activity and catalytic stability.

2.3. Coke Analysis

Coke formation during the propane dehydrogenation process is an inherent factor which adversely affects the catalytic performance [11]. Figure 12 depicts the amount of coke calculated from TG analysis of the spent catalysts after a propane dehydrogenation reaction for 120 min at 620 °C. As can be seen, the PtSnIn/1.5Ce-Al catalyst possesses the lowest coke amount, indicating that Ce species can reduce the accumulation of coke. The outstanding stability and selectivity of the PtSnIn/1.5Ce-Al catalyst are ascribed to it having the lowest amount of coke. Similar results were also displayed by Damyanova et al. [40]. The synergistic interplay between Pt and CeO2 enhances the stability of Pt nanoparticles, resulting in reduced deep dehydrogenation and minimized carbon deposition on the catalyst surface [27].

3. Experimental Section

3.1. Catalyst Preparation

The PtSnIn/xCe-Al catalysts were prepared in the laboratory using a sequential impregnation method. Commercial γ-Al2O3 powder (SBET ≥ 200 m2/g, 60–80 mesh, denoted as Al) was employed as the catalyst support. The preparation process involved the following steps:
  • Ce Impregnation: The γ-Al2O3 support was first impregnated with an aqueous solution of Ce(NO3)3.
  • Sn and In Impregnation: The Ce-impregnated support was then treated with a mixed ethanol solution containing SnCl2 (≥98.0%) and In(NO3)3 (≥99.5%).
  • Pt Impregnation: Finally, the sample was impregnated with an aqueous solution of H2PtCl6.
The impregnation sequency of Ce, Sn, In, and Pt can be referred to in the literature [38,43].
After each impregnation step, the sample was dried at 120 °C for 10 h and subsequently calcined in air at 550 °C for 4 h. A series of catalysts with varying Ce loadings were prepared and labeled as PtSnIn/xCe-Al, where x represents the mass percentage of Ce. For reference, Pt/Al and PtSn/Al samples were also prepared using the same method. The nominal loadings of Pt, Sn, and In in all catalysts were fixed at 0.3 wt.%, 0.6 wt.%, and 1.5 wt.%, respectively. All the samples were sieved into particles of 60–80 mesh size for further study. All chemical reagents used in this study were purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China).

3.2. Catalyst Characterizations

The structural properties of the catalyst were measured by a N2 physical adsorption instrument (NOVA 4000, Quantachrome, Boynton Beach, FL, USA) at −196 °C. Before the analysis procedure, the sample was degassed at 200 °C to remove impurities on the catalyst surface and inside the pores. The powder X-ray diffraction (XRD) patterns were collected with a Brucker diffractometer (D/max-RA) employing Cu Kα (40 kV, 40 mA). Temperature-programmed desorption of ammonia (NH3-TPD) was performed on an automatic chemical adsorption instrument. The samples were pretreated at 500 °C for 1 h in helium (He) flow prior to each experiment. Then, the samples were cooled to 50 °C and saturated with ammonia. NH3-TPD was conducted from 100 to 500 °C. The temperature-programmed reduction (TPR) experiments for the fresh catalysts were implemented using a Quantachrome Autosorb-IQ gas adsorption analyzer. H2-temperature-programmed reduction (H2-TPR) was carried out with a conventional flow apparatus equipped with a thermal conductivity detector (TCD). The samples were pretreated at 300 °C for 1 h in a flow of argon (Ar), then were cooled to 25 °C. Finally, the profile was recorded by measuring H2 consumption from 50 °C to the target temperature with a ramp of 10 °C/min. The X-ray photoelectron spectroscopy (XPS) characterization was implemented on a V.G. Scientific Escalab 250 with Al Kα radiation as the excitation source and using a binding energy of the C 1s line (284.6 eV) to calibrate the electron binding energies. Transmission electron microscopy (TEM) images were obtained with a transmission electron microscope (TEM; JEOL JEM2010, JEOL. Ltd., Tokyo, Japan). The thermogravimetric (TG) analysis of the spent catalysts was carried out in air flow (50 mL/min) with an LCT thermogravimetric analyzer (DTG-60H) from room temperature to 700 °C at a rate of 10 °C/min. The catalysts were placed in a crucible using Al2O3 as a reference.

3.3. Propane Dehydrogenation Reaction

Propane dehydrogenation is an equilibrium endothermic reaction (1). The thermodynamic analysis presents that the equilibrium conversion decreases exponentially with pressure, suggesting that the reduction in hydrocarbon partial pressure is conducive to improving conversion [9]. To reduce the hydrocarbon partial pressure, 14% hydrogen and 70% argon (volume fraction) were introduced to dilute the reacting mixture. Furthermore, to obtain high propane conversions, a high operating temperature (>600 °C) is indispensable.
C3H8 ⇌ C3H6 + H2, ΔH°25°C = 124.6 KJ/mol
The catalytic performance of the prepared catalysts for PDH was evaluated in a fixed-bed tubular quartz reactor operating at atmospheric pressure and a reaction temperature of 620 °C. The reaction feed consisted of a gas mixture containing 16% propane and 14% H2, with a total flow rate of 50 mL·min−1. The weight hourly space velocity (WHSV) was maintained at 3.3 h−1. Prior to the reaction, the catalyst (0.3 g, sieved to 60–80 mesh) was pre-reduced in situ under a flow of pure H2 (11.2 mL/min) at 580 °C for 2.5 h to activate the active sites. After activation, the reaction was initiated by introducing the propane–hydrogen–argon mixture into the reactor. The composition of the feed and reaction products was analyzed using an online gas chromatography system (GC, SP-6980, Shanghai, China) equipped with a flame ionization detector (FID) and an AT-PLOT PORA-Q capillary column. Propane conversion was calculated as the percentage of propane converted into all reaction products, while propylene selectivity was defined as the obtained amount of propylene divided by the amount of reactant converted to all products. The propane conversion and propylene selectivity were on the basis of the total number of the carbon atom balance.

4. Conclusions

In this study, PtSnIn/xCe-Al catalysts were successfully prepared via a sequential impregnation method and evaluated for propane dehydrogenation. The structural and catalytic properties were systematically investigated using multiple characterization techniques. XRD and BET analyses revealed that Ce species partially exist as CeAlO3 in the reduced catalysts, enhancing the thermal stability of the alumina support. NH3-TPD results demonstrated that the incorporation of Ce effectively reduces the total acidity of the PtSnIn/xCe-Al catalysts. TEM characterization indicated that the catalyst with 1.5 wt.% Ce loading exhibited superior Pt nanoparticle dispersion, with an average particle size of 8 nm. TPR and XPS analyses further elucidated that Ce modifies the interaction between metal species and the support, leading to an increased presence of oxidized-state Sn species on the catalyst surface. The catalytic performance for propane dehydrogenation was significantly improved with the addition of 0.5–1.5 wt.% Ce. Notably, the PtSnIn/1.5Ce-Al catalyst achieved an initial propane conversion of 62.6% and maintained a conversion of 57.2% after a 120 min reaction. Moreover, the catalyst exhibits splendid stability, with only a slight decline of ~2% after four reaction–regeneration cycles and above 40.0% conversion after 53 h of continuous operation. These findings highlight the critical role of Ce in optimizing the structural and catalytic properties of PtSnIn/xCe-Al catalysts, making them promising candidates for propane dehydrogenation applications.

Author Contributions

Writing—original draft, J.L. and K.X.; writing—review and editing, F.Z. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Data Availability Statement

All the data are contained within the article.

Conflicts of Interest

The authors declare no conflicts of interest.

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Catalysts 15 00506 g001
Figure 1. XRD patterns of the reduced catalysts.
Figure 1. XRD patterns of the reduced catalysts.
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Figure 2. NH3-TPD profiles of the samples.
Figure 2. NH3-TPD profiles of the samples.
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Figure 3. H2-TPR profiles of the catalysts.
Figure 3. H2-TPR profiles of the catalysts.
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Figure 4. Sn3d5/2 XPS spectra of the PtSnIn/0.0Ce-Al and PtSnIn/1.5Ce-Al catalysts.
Figure 4. Sn3d5/2 XPS spectra of the PtSnIn/0.0Ce-Al and PtSnIn/1.5Ce-Al catalysts.
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Catalysts 15 00506 g005
Figure 5. In3d5/2 XPS spectra of the PtSnIn/0.0Ce-Al and PtSnIn/1.5Ce-Al catalysts.
Figure 5. In3d5/2 XPS spectra of the PtSnIn/0.0Ce-Al and PtSnIn/1.5Ce-Al catalysts.
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Figure 6. Ce3d XPS spectra of the PtSnIn/1.5Ce-Al catalyst.
Figure 6. Ce3d XPS spectra of the PtSnIn/1.5Ce-Al catalyst.
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Figure 7. TEM images and corresponding Pt particle size distribution of the reduced PtSnIn/xCe-Al catalysts: (a) PtSnIn/0.0Ce-Al; (b) PtSnIn/1.5Ce-Al; (c) PtSnIn/2.5Ce-Al.
Figure 7. TEM images and corresponding Pt particle size distribution of the reduced PtSnIn/xCe-Al catalysts: (a) PtSnIn/0.0Ce-Al; (b) PtSnIn/1.5Ce-Al; (c) PtSnIn/2.5Ce-Al.
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Catalysts 15 00506 g008
Figure 8. Effect of metallic compositions of catalysts on the catalytic performances for propane dehydrogenation (reaction conditions: T = 620 °C; H2/C3H8 molar ratio = 7:8; WHSV = 3.3 h−1; mcat. = 0.3 g).
Figure 8. Effect of metallic compositions of catalysts on the catalytic performances for propane dehydrogenation (reaction conditions: T = 620 °C; H2/C3H8 molar ratio = 7:8; WHSV = 3.3 h−1; mcat. = 0.3 g).
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Figure 9. Effect of Ce loading of PtSnIn/xCe-Al catalysts on the catalytic performances for propane dehydrogenation (reaction conditions: T = 620 °C; H2/C3H8 molar ratio = 7:8; WHSV = 3.3 h−1; mcat = 0.3 g).
Figure 9. Effect of Ce loading of PtSnIn/xCe-Al catalysts on the catalytic performances for propane dehydrogenation (reaction conditions: T = 620 °C; H2/C3H8 molar ratio = 7:8; WHSV = 3.3 h−1; mcat = 0.3 g).
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Figure 10. The catalytic performances of the PtSnIn/1.5Ce-Al catalyst within 4 reaction–regeneration cycles (reaction conditions: T = 620 °C; H2/C3H8 molar ratio = 7:8; WHSV = 3.3 h−1; mcat = 0.3 g).
Figure 10. The catalytic performances of the PtSnIn/1.5Ce-Al catalyst within 4 reaction–regeneration cycles (reaction conditions: T = 620 °C; H2/C3H8 molar ratio = 7:8; WHSV = 3.3 h−1; mcat = 0.3 g).
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Figure 11. Stability test of the PtSnIn/1.5Ce-Al catalyst in propane dehydrogenation (reaction conditions: T = 620 °C; H2/C3H8 molar ratio = 7:8; WHSV = 3.3 h−1; mcat. = 0.3 g).
Figure 11. Stability test of the PtSnIn/1.5Ce-Al catalyst in propane dehydrogenation (reaction conditions: T = 620 °C; H2/C3H8 molar ratio = 7:8; WHSV = 3.3 h−1; mcat. = 0.3 g).
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Figure 12. Amounts of coke in the spent catalysts after a propane dehydrogenation reaction for 120 min at 620 °C.
Figure 12. Amounts of coke in the spent catalysts after a propane dehydrogenation reaction for 120 min at 620 °C.
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Table 1. The textural properties of the reduced PtSnIn/xCe-Al catalysts.
Table 1. The textural properties of the reduced PtSnIn/xCe-Al catalysts.
SampleS BET (m2g−1)V P (cm3g−1)Dpore (nm)Average Pt Particle Size (nm)
Al200.8440.4726.655/
PtSnIn/0.0Ce-Al181.8670.4366.66210.8
PtSnIn/0.5Ce-Al188.0470.4895.980-
PtSnIn/1.5Ce-Al191.7940.4816.6208.0
PtSnIn/2.5Ce-Al184.8990.4665.45011.3
Table 2. Results of NH3-TPD measurement.
Table 2. Results of NH3-TPD measurement.
SampleTm (°C)Total Area (a.u.)Peak Area Fraction (%)
IIIIIIIIIIII
Al184222285120.58122959
PtSnIn/0.0Ce-Al16320427991.94354223
PtSnIn/1.5Ce-Al18422026970.55363331
Table 3. Summary of XPS results.
Table 3. Summary of XPS results.
CatalystBinding Energy (eV)
Sn 3d5/2In 3d5/2
PtSnIn/Al485.7 (26%);
486.6 (40%);
487.5 (34%);		444.1 (30%)
445.2 (70%)
PtSnIn/1.5Ce-Al485.2 (14%);
486.7 (50%);
487.6 (36%);		444.4 (31%)
445.3 (69%)
Table 4. Comparison with the published Pt-based catalysts used in PDH reactions.
Table 4. Comparison with the published Pt-based catalysts used in PDH reactions.
CatalystPt wt. %Reaction ConditionsTime on Stream Test (h)Propane Conversion (%)Propylene Selectivity (%)Ref.
InPt/Sn-SBA-151580 °C
C3H8/Ar = 1/4
WHSV = 4.05 h−1		3340.999.0[50]
Pt-Sn/B-ZrO2-100.35550 °C
C3H8/H2/N2 = 1/1/8
WHSV = 3 h−1		535.099.5[51]
Pt-Ir/Mg(Al)O1.91600 °C
C3H8/H2/He = 1/1/8
WHSV = 51.9 h−1		0.517.588.7[52]
Pt-Sn/CeO21680 °C
C3H8/H2 = 16.7/83.3
WHSV = 2.2 h−1		634.685.7[53]
SnPt_10B20S70A0.5550 °C
C3H8/H2O = 4/1
WHSV = 4 h−1		2421.996.2[54]
Pt-Sn/Al2O33600 °C
C3H8/H2/N2 = 3/3/7
WHSV = 8.9 h−1		532.994.0[55]
Pt-Sn-K-Co0.3-Zn0.7/γ-Al2O30.5620 °C
C3H8/H2 = 1.2/1 WHSV = 2 h−1		1042.790.0[31]
K-PtSn@MFI0.4600 °C
C3H8/N2 = 5/16
WHSV = 1.85 h−1		6547.297.5[56]
PtIn/LaAlO/AlO0.6600 °C
C3H8/H2/N2 = 8/7/35
WHSV = 3 h−1		1627.890.0[57]
PtSn-Mg(3Zn)AlO0.5550 °C
C3H8/H2/N2 = 20/3/80
WHSV = 6.3 h−1		1443.799.5[58]
PtSnIn/1.5Ce-Al0.3620 °C
C3H8/H2/Ar = 8/7/35
WHSV = 3.3 h−1		5340.096.0This work
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Liu, J.; Xia, K.; Zhang, F. Enhancing Propane Dehydrogenation Performance on Cerium-Modified PtSnIn/Al Trimetallic Catalysts. Catalysts 2025, 15, 506. https://doi.org/10.3390/catal15050506

AMA Style

Liu J, Xia K, Zhang F. Enhancing Propane Dehydrogenation Performance on Cerium-Modified PtSnIn/Al Trimetallic Catalysts. Catalysts. 2025; 15(5):506. https://doi.org/10.3390/catal15050506

Chicago/Turabian Style

Liu, Jinbao, Ke Xia, and Fen Zhang. 2025. "Enhancing Propane Dehydrogenation Performance on Cerium-Modified PtSnIn/Al Trimetallic Catalysts" Catalysts 15, no. 5: 506. https://doi.org/10.3390/catal15050506

APA Style

Liu, J., Xia, K., & Zhang, F. (2025). Enhancing Propane Dehydrogenation Performance on Cerium-Modified PtSnIn/Al Trimetallic Catalysts. Catalysts, 15(5), 506. https://doi.org/10.3390/catal15050506

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