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. 2025 Apr 15;10(16):16993–17004. doi: 10.1021/acsomega.5c01829

Support Effects on the Activity and Selectivity of Ni3CuSn0.3 Trimetallic Catalysts in the Selective Hydrogenation of Phenylacetylene

Kehang Ruan a, Aohui Xiao a, Hongjie Cui b, Zhiming Zhou a,*
PMCID: PMC12044564  PMID: 40321504

Abstract

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Supported Ni-based catalysts present a promising alternative to precious Pd-based catalysts for the selective hydrogenation of phenylacetylene due to their abundance and cost-effectiveness. However, the influence of support materials on the catalytic performance of Ni-based catalysts has been insufficiently explored. In this study, a series of Ni3CuSn0.3 trimetallic catalysts (Ni:Cu:Sn molar ratio of 3:1:0.3; Ni loading of 20 wt %) supported on various materials, including SiO2, SBA-15, Al2O3, MgO, CeO2, and TiO2, were synthesized, characterized, and evaluated. In general, silica-supported catalysts showed higher hydrogenation activity but lower styrene selectivity, while metal oxide-supported catalysts exhibited reduced activity but enhanced selectivity. The catalytic activity decreased with increasing Sn incorporation into the Ni–Cu alloys, whereas styrene selectivity was affected by both electronic and geometric effects. Among the catalysts tested, Ni3CuSn0.3/Al2O3 demonstrated the highest styrene selectivity at complete phenylacetylene conversion. This catalyst was further prepared via a scalable solvent-free ball milling method, achieving an initial reaction rate of 4.5 mmol/(g·min) and 95% styrene selectivity at complete phenylacetylene conversion under 60 °C and 0.5 MPa. Moreover, it displayed stable performance over multiple reaction cycles, with the properties remaining well-preserved. These results offer new opportunities for developing large-scale processes for the selective hydrogenation of phenylacetylene using earth-abundant catalysts.

1. Introduction

Styrene is an important industrial monomer used in the production of plastics such as polystyrene, styrene-acrylonitrile and acrylonitrile-butadiene-styrene copolymers, and poly(phenylene oxide)-polystyrene.1 The primary method for styrene production is the direct dehydrogenation of ethylbenzene, which accounts for 85% of commercial production.2 Other routes include the coproduction of styrene and propylene oxide and the recovery of styrene from pyrolysis gasoline. Except for the styrene-propylene oxide process, crude styrene typically contains a small amount of phenylacetylene. This impurity must be removed through hydrogenation, because it can poison downstream polymerization catalysts and negatively influence the quality of the polymers.3−5

Solid catalysts are essential in phenylacetylene hydrogenation. Ideal catalysts possess a high reaction rate, superior styrene selectivity, and long-term stability. These properties ensure complete conversion of phenylacetylene while minimizing styrene hydrogenation to ethylbenzene, thereby preserving styrene yield. Precious metal-based catalysts, particularly monometallic Pd catalysts, exhibit high hydrogenation activity but often suffer from low styrene selectivity as phenylacetylene approaches complete conversion.6−10 Moreover, the high cost and limited availability of Pd pose significant constraints. Therefore, considerable attention has shifted toward the development of nonprecious metal-based catalysts, with Ni-based catalysts receiving particular attention due to their cost-effectiveness, abundance, and superior activity compared to other nonprecious metal alternatives.11−17

Various materials have been explored as supports for Ni-based catalysts. Donphai et al. studied Ni-carbon nanofibers supported on mesocellular silica and reported a styrene selectivity of about 90% at 90.8% phenylacetylene conversion under 80 °C and 0.1 MPa.18 Yang et al. demonstrated a styrene selectivity of around 80% at 99% phenylacetylene conversion using Ni2Si/SBA-15 under 40 °C and 1.0 MPa.19 Recently, we achieved a high styrene selectivity of approximately 93% at complete phenylacetylene conversion under 60 °C and 0.5 MPa with Ni3CuSn0.3/SiO2.20 Note that these catalysts utilized silica-based supports. In addition, metal oxide supports have been employed for selective hydrogenation of phenylacetylene. Chen et al. synthesized a Ni2P/Al2O3 catalyst, achieving a styrene selectivity of 88.2% at 98.6% phenylacetylene conversion under 100 °C and 0.3 MPa.21 Liu et al. reported a styrene selectivity of 89% at complete phenylacetylene conversion under 40 °C and 0.5 MPa with Ni3Sn/MgAl2O4.22 Bao et al. achieved a styrene selectivity of 92% at complete phenylacetylene conversion under 60 °C and 0.5 MPa using NiZn3/Al2O3.23 Li et al. obtained an impressive styrene selectivity of 96% at complete phenylacetylene conversion over Ni2P/TiO2 under 80 °C and 0.1 MPa in the presence of visible light irradiation.24 The reviewed literature demonstrates varying results for the selective hydrogenation of phenylacetylene over different supports. However, direct comparison of these supports is challenging due to variations in factors such as catalyst preparation methods, metal composition, Ni loading, and testing conditions.

Considering the critical role of supports, this study aims to investigate and compare the effects of various support materials on the selective hydrogenation of phenylacetylene. Representative supports, including SiO2, SBA-15, Al2O3, MgO, CeO2, and TiO2, are evaluated. A combination of Ni, Cu, and Sn metals in a molar ratio of 3:1:0.3 is immobilized onto these supports using the wet impregnation method, because our previous study demonstrated its good catalytic performance in phenylacetylene hydrogenation.20 The effects of support textural properties and metal–support interactions on the crystal phase structure, metal particle size, and electronic state of Ni, Cu, and Sn are systematically examined. In addition, a solvent-free ball milling technique is used to prepare the optimized Ni-based catalyst, which enhances its potential for industrial applications owing to its scalability and economic viability.

2. Experimental Section

2.1. Catalyst Preparation

Unless specified otherwise, the supported Ni3CuSn0.3 catalysts were prepared via the wet impregnation method.20 Regarding the support materials, Al2O3, MgO, and two types of SiO2 were purchased from Makclin Biochemical Co., Ltd., while SBA-15,25 TiO2,26 and CeO227 were synthesized following methods reported in the literature. Taking Ni3CuSn0.3/SiO2 as an example, 0.721 g of Ni(NO3)2·6H2O, 0.200 g of Cu(NO3)2·3H2O, and 0.087 g of SnCl4·5H2O were dissolved in 30 mL of deionized water and stirred at room temperature for 1 h. Next, 0.5 g of SiO2 was added to the solution and the mixture was stirred for 10 h. The solvent was then removed from the suspension using a rotary evaporator at 70 °C. The resulting solid was dried in an oven at 120 °C for 10 h, ground into a fine powder, and calcined in a muffle furnace at 500 °C for 2 h with a heating rate of 5 °C/min. Finally, the calcined catalyst powder was reduced in a tube furnace under a 10% H2/N2 flow (50 mL/min) at 500 °C for 2 h with a heating rate of 10 °C/min. The resulting catalyst had a nominal Ni loading of 20 wt % and a Ni:Cu:Sn molar ratio of 3:1:0.3.

The optimal catalyst was further prepared using a solvent-free ball milling technique. The metal precursors and support material (in the same quantities as mentioned above) were mixed in a planetary ball mill at 300 rpm for 4 h. The resulting mixture was subsequently subjected to drying, calcination, and reduction treatments, identical to the procedures described earlier.

2.2. Catalyst Characterization

The crystal phase structures of the catalysts were examined using X-ray diffraction (XRD) on a Bruker D8 Advance diffractometer with Cu Kα radiation (λ = 1.5406 Å), scanning over a 2θ range of 10–80°. The specific surface area, pore volume, and average pore diameter were determined via N2 physisorption measurements at −196 °C using a Micromeritics ASAP 2420 instrument. The Ni, Cu, and Sn contents in the catalysts were quantified by inductively coupled plasma optical emission spectrometry (ICP-OES, Agilent 725-ES). H2 temperature-programmed reduction (H2-TPR) was conducted using a Micromeritics AutoChem 2920. About 50 mg of sample was heated from room temperature to 800 °C at 10 °C/min under a 10% H2/N2 flow (30 mL/min), while H2 consumption was monitored by a thermal conductivity detector. The microstructures of the catalysts were investigated through high-resolution transmission electron microscopy (HRTEM, JEOL JEM-2100F). Elemental distribution was further analyzed via energy-dispersive spectroscopy (EDS, Oxford system) coupled with the HRTEM. X-ray photoelectron spectroscopy (XPS) measurements were performed using a Thermo Scientific ESCALAB 250Xi instrument with an Al Kα radiation source (1486.6 eV) and a pass energy of 40 eV. The binding energies were calibrated using the C 1s peak at 284.8 eV.

2.3. Catalyst Test

The selective hydrogenation of phenylacetylene was conducted in a mechanically stirred 300 mL semibatch tank reactor (Parr 5100). The reaction mixture consisted of 0.15 g of reduced catalyst, 5 g of phenylacetylene, 5 g of n-octane (used as an internal standard), and 90 g of ethanol (solvent). Ethanol was selected as the solvent based on previous studies,28,29 which have demonstrated its superiority over other solvents (e.g., n-hexane, cyclohexane, toluene, tetrahydrofuran, ethyl acetate, chloroform, dioxane, methanol, and isopropanol) for achieving optimal performance in the selective hydrogenation of phenylacetylene. Additionally, ethanol offers advantages such as low toxicity and wide availability, making it a practical and environmentally friendly choice for this study. The reactor was initially purged with N2, and the system was heated to 60 °C. Once the temperature stabilized, the N2 was replaced by H2 through five successive purging cycles to ensure a hydrogen atmosphere. The reaction was initiated at 60 °C and 0.5 MPa under continuous stirring at 1000 rpm. At specified time intervals, around 1 mL of the reaction solution was sampled for analysis. Product concentrations were determined using gas chromatography equipped with a capillary column (PEG-20M, 30 m × 0.32 mm × 0.50 μm) and a flame ionization detector. For all catalysts evaluated in this study, the hydrogenation products of phenylacetylene consisted exclusively of styrene and ethylbenzene, with no other byproducts detected.

Phenylacetylene conversion is calculated as the ratio of reacted moles of phenylacetylene to the initial moles of phenylacetylene loaded into the reactor. Styrene selectivity is determined by dividing the moles of styrene in the product by the reacted moles of phenylacetylene. Styrene yield is calculated as the product of phenylacetylene conversion and styrene selectivity. The initial hydrogenation rate is defined as the moles of phenylacetylene converted per unit time per unit mass of catalyst during the initial hydrogenation period. This rate is calculated from data where the conversion is below 20%.

3. Results and Discussion

3.1. Silica-Supported Ni3CuSn0.3 Catalysts

Figure 1 shows the N2 adsorption isotherms and pore size distribution curves for SiO2(1), SiO2(2) and SBA-15, along with their corresponding catalysts. The specific surface area, pore volume and average pore diameter of each sample are summarized in Table 1. All supports and catalysts display type IV isotherms with a distinct hysteresis loop, indicating the presence of mesoporous structures.30 The catalysts show smaller specific surface areas and pore volumes compared to their respective supports, implying successful immobilization of metal particles on the supports. This is confirmed by the measured Ni:Cu:Sn atomic ratios for each catalyst, which closely align with their nominal values (Table 1). Although all supports are silica-based materials, they exhibit different textural properties, which influence the textural characteristics of the resulting catalysts. SiO2(2) features large pores, retaining 78% of its pore volume after metal loading. In contrast, SBA-15, characterized by small and uniform pores, experiences a significant reduction in pore volume, retaining only 48% after metal loading. SiO2(1), with a slightly larger average pore diameter and a broader pore size distribution than SBA-15, shows an intermediate pore volume retention of 60% after metal loading.

Figure 1.

Figure 1

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(a,c) N2 adsorption–desorption isotherms and (b,d) pore size distribution curves of (a,b) silica supports and (c,d) silica-supported catalysts.

Table 1. Textural Properties, Metal Loadings, and Catalytic Performance of Various Catalysts.

        Metal loading (wt %)b
     Other datad
Samples SBET (m2/g) Vpa (cm3/g) dpa (nm) Ni Cu Sn Ni:Cu:Snb rPAc (mmol/(g·min) t (min) α (%) S (%) Y (%)
SiO2(1) 379.2 0.88 7.8                  
Ni3CuSn0.3/SiO2(1) 254.7 0.53 7.3 19.3 6.6 3.7 3.17:1:0.30 5.7 65 99.3 92.8 92.2
SiO2(2) 359.2 0.94 13.9                  
Ni3CuSn0.3/SiO2(2) 204.6 0.73 15.1 20.4 7.5 4.3 2.95:1:0.31 4.7 79 99.4 92.4 91.8
SBA-15 753.1 1.23 7.3                  
Ni3CuSn0.3/SBA-15 377.4 0.59 5.6 19.6 6.9 3.9 3.07:1:0.30 7.0 45 99.2 91.9 91.2
Al2O3 88.0 0.26 8.8                  
Ni3CuSn0.3/Al2O3 62.8 0.18 8.7 19.5 7.1 3.6 2.97:1:0.27 1.7 200 99.4 94.1 93.5
MgO 27.1 0.19 29.0                  
Ni3CuSn0.3/MgO 28.6 0.15 24.8 20.4 7.5 4.1 2.95:1:0.29 1.6 210 99.1 92.4 91.6
CeO2 178.1 0.36 7.0                  
Ni3CuSn0.3/CeO2 66.7 0.20 9.9 19.9 6.9 3.8 3.12:1:0.29 2.1 160 99.1 93.1 92.3
TiO2 126.9 0.44 12.2                  
Ni3CuSn0.3/TiO2 28.0 0.20 31.8 20.3 7.2 3.6 3.05:1:0.27 0.5 660 99.1 93.2 92.4
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a

Pore volume (Vp) and average pore diameter (dp) were acquired from the desorption branch by the BJH method.

b

Metal loadings and atomic ratios were determined by ICP-OES.

c

Initial hydrogenation rates were calculated using data corresponding to conversions below 20%.

d

These data were obtained at phenylacetylene conversions exceeding 99% (t: reaction time; α: phenylacetylene conversion; S: styrene selectivity; Y: styrene yield).

Figure 2 shows the H2-TPR profiles of silica-supported Ni3CuSn0.3 catalysts. For comparison, the profiles of unsupported Ni3Cu, Ni3Sn0.3, and Ni3CuSn0.3, prepared using the same method as the supported catalysts, are also included. Ni3Cu exhibits a broad peak within the range of 150–300 °C, which corresponds to the reduction of nickel and copper oxides.31,32 In the case of Ni3Sn0.3, peaks between 340 and 480 °C are associated with the reduction of nickel and tin oxides.33,34 For Ni3CuSn0.3, three peaks are identified. The first peak centered at 190 °C is attributed to the reduction of Ni–Cu oxides, while the third peak at 405 °C is linked to the reduction of Ni–Sn oxides. The second peak (the main peak), located at 330 °C, lies between the reduction temperatures of Ni3Cu and Ni3Sn0.3 and can be assigned to the reduction of Ni–Cu–Sn mixed oxides. Upon metal loading onto the support, each supported Ni3CuSn0.3 catalyst displays three reduction peaks similar to those of unsupported Ni3CuSn0.3. However, the peak temperatures vary between the supported and unsupported samples. The main reduction peak of the supported Ni3CuSn0.3 shifts to a lower temperature (250–270 °C) compared to the unsupported Ni3CuSn0.3. This shift is likely due to the smaller metal particle size resulting from the dispersion effect of the silica support. Further analysis of the supported catalysts reveals different reduction behaviors. The reduction peak belonging to Ni–Sn oxides is relatively small for Ni3CuSn0.3/SiO2(2) but noticeably larger for Ni3CuSn0.3/SiO2(1). Conversely, the main peak of Ni3CuSn0.3/SiO2(2) is larger than that of Ni3CuSn0.3/SiO2(1). These findings suggest that a higher proportion of tin oxides in Ni3CuSn0.3/SiO2(2) interacts with nickel and copper oxides, leading to their simultaneous reduction.

Figure 2.

Figure 2

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H2-TPR profiles of silica-supported catalysts (the intensities for Ni3Cu, Ni3Sn0.3, and Ni3CuSn0.3 are scaled by a factor of 0.5 for clear comparison).

Figure 3 presents the XRD patterns of unsupported Ni3Cu, Ni3Sn0.3 and Ni3CuSn0.3 as well as silica-supported catalysts after H2 reduction. For the bimetallic Ni3Cu, three diffraction peaks are observed at 2θ = 44.4, 51.7, and 76.0°. These peaks are positioned between the Ni(111) (44.5°, PDF#87–0712) and Cu(111) (43.3°, PDF#04–0836) reflections, between Ni(200) (51.8°) and Cu(200)(50.4°), and between Ni(220) (76.3°) and Cu(220) (74.1°), respectively. This implies the formation of Ni–Cu solid solution alloys. For Ni3Sn0.3, diffraction peaks are observed at 2θ = 28.9, 34.1, 39.5, 42.8, 45.1, 59.5, and 71.4°. These peaks closely match but are slightly shifted to higher angles (by about 0.2°) relative to those of Ni3Sn intermetallics (PDF#35–1362). Considering the complex crystal structures of Ni–Sn alloys,35 these peaks are attributed to quasi-Ni3Sn alloys. Other peaks of Ni3Sn0.3 are assigned to metallic Ni. For the trimetallic Ni3CuSn0.3, the diffraction peaks appear similar to those of Ni3Sn0.3 but differ slightly in their positions. Within the enlarged 2θ range of 42–46°, the peaks at 42.8 and 45.1°, corresponding to the (002) and (201) planes of quasi-Ni3Sn alloy, shift to higher angles for Ni3CuSn0.3. This shift can be ascribed to lattice contraction derived from the substitution of Sn by Cu, as the atomic radius of Cu (1.278 Å) is smaller than that of Sn (1.620 Å).36 On the other hand, the main peak of Ni3Cu (44.4°) shifts to 44.3° for Ni3CuSn0.3, indicating lattice expansion due to the substitution of Cu by Sn. These findings suggest the successful formation of Ni–Cu–Sn trimetallic alloys through the mutual substitution of Sn and Cu in the Ni–Sn and Ni–Cu alloy structures.

Figure 3.

Figure 3

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XRD patterns of reduced silica-supported catalysts at (a) 2θ = 10–80° and (b) 2θ = 42–46° (the intensities for Ni3Cu, Ni3Sn0.3, and Ni3CuSn0.3 are scaled by factors of 0.1, 0.25, and 0.5, respectively).

For silica-supported catalysts, a broad peak in the range of 15–30° is observed, which belongs to the amorphous SiO2.37 In addition, three distinct peaks associated with Ni–Cu–Sn alloys are present, with positions shifted to smaller angles compared to unsupported Ni3CuSn0.3. Notably, the main peak of Ni3CuSn0.3/SiO2(2) shows the largest shift (to 43.6°), implying a higher degree of Sn incorporation into the Ni–Cu alloy structure. This observation is consistent with the H2-TPR analysis, which indicates enhanced interaction among Ni, Cu and Sn oxides in Ni3CuSn0.3/SiO2(2). Further evidence of Ni–Cu–Sn alloy formation in supported catalysts is provided by HRTEM analysis (Figure S1). Lattice spacings of 0.185, 0.205, and 0.206 nm are detected, which do not correspond to those of Ni(200) (0.176 nm), Ni(111) (0.204 nm), Cu(200) (0.181 nm), or Cu(111) (0.209 nm). Additionally, these lattice spacings do not match those of Ni3Sn. The metal particles are well dispersed on the silica support, with average particle sizes of 23.6, 18.4, and 11.8 nm for Ni3CuSn0.3/SiO2(1), Ni3CuSn0.3/SiO2(2), and Ni3CuSn0.3/SBA-15, respectively (Figure S1). The small metal particle size of Ni3CuSn0.3/SBA-15 is attributed to the high specific surface area of SBA-15.

Figure 4 compares the catalytic performance of unsupported and three silica-supported catalysts in terms of phenylacetylene conversion and styrene selectivity. Unsupported Ni3CuSn0.3 shows negligible activity for phenylacetylene hydrogenation, highlighting the critical role of the support in promoting the dispersion of Ni3CuSn0.3 metal particles. The time required for complete phenylacetylene conversion is 45 min for Ni3CuSn0.3/SBA-15, 65 min for Ni3CuSn0.3/SiO2(1), and 79 min for Ni3CuSn0.3/SiO2(2). Moreover, the initial hydrogenation rates, calculated based on conversions below 20%, are 7.0, 5.7, and 4.7 mmol/(g·min), respectively (Table 1). Apparently, Ni3CuSn0.3/SBA-15 exhibits the highest activity among the three catalysts, probably due to its much smaller metal particle size. In contrast, although Ni3CuSn0.3/SiO2(2) has smaller metal particles than Ni3CuSn0.3/SiO2(1), its apparent activity is lower. This discrepancy may be related to the increased incorporation of Sn into the Ni–Cu alloy structure in Ni3CuSn0.3/SiO2(2). Previous studies have shown that the hydrogenation activity of Ni3CuSnx catalysts decreases as the Sn content (or the extent of Cu substitution by Sn) increases.20,38 It should be noted that the active surface areas of these catalysts could not be determined using H2 or CO chemisorption, despite multiple attempts. Similar results were observed for the subsequent metal oxide-supported catalysts.

Figure 4.

Figure 4

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(a) Phenylacetylene conversion vs reaction time, and (b) styrene selectivity vs phenylacetylene conversion obtained for unsupported Ni3CuSn0.3 and silica-supported Ni3CuSn0.3 catalysts.

Ni3CuSn0.3/SiO2(2) exhibits slightly higher styrene selectivity than Ni3CuSn0.3/SiO2(1), with both outperforming Ni3CuSn0.3/SBA-15. This inverse relationship between activity and selectivity highlights the performance trade-off in silica-supported Ni3CuSn0.3 catalysts. Overall, all three catalysts show high selectivity throughout the hydrogenation process, achieving styrene selectivity of 92.8%, 92.4%, and 91.9%, along with styrene yields of 92.2%, 91.8%, 91.2% at complete phenylacetylene conversion for Ni3CuSn0.3/SiO2(1), Ni3CuSn0.3/SiO2(2), and Ni3CuSn0.3/SBA-15, respectively. The reliability of the data is verified by conducting the performance test twice. As shown in Figure S2, the results from the two runs for two representative catalysts are highly consistent. For each data point, the absolute error in styrene selectivity between the two runs is less than 0.2%.

3.2. Metal Oxide-Supported Ni3CuSn0.3 Catalysts

Similar to silica-supported catalysts, Al2O3, MgO, CeO2 and TiO2 supports, as well as their respective Ni3CuSn0.3 catalysts, exhibit hysteresis loops characteristic of mesoporous structures, as shown in Figure 5. However, both the metal oxide supports and their corresponding catalysts display lower surface areas and pore volumes compared to silica and silica-supported catalysts. Upon metal loading, the specific surface area and pore volume of the metal oxide supports decrease (Table 1). In particular, TiO2 shows a substantial reduction in surface area (from 126.9 to 28.0 m2/g) and pore volume (from 0.44 to 0.20 cm2/g), accompanied by a marked increase in pore diameter (from 12.2 to 31.8 nm). This change can be attributed to the blockage of small pores (<10 nm) by metal particles, as evidenced by the pore size distribution curves of TiO2 and Ni3CuSn0.3/TiO2. In contrast, the pore size distribution features of Al2O3, MgO and CeO2 remain largely unchanged before and after metal loading, although their peak intensities decrease after metal loading.

Figure 5.

Figure 5

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(a,c) N2 adsorption–desorption isotherms and (b,d) pore size distributions curves of (a,b) metal oxide supports and (c,d) metal oxide-supported catalysts.

In contrast to the similar H2-TPR profiles observed for all silica-supported catalysts, the metal oxide-supported Ni3CuSn0.3 catalysts display distinct profiles (Figure 6a), indicating different metal–support interactions. The profile of Ni3CuSn0.3/CeO2 is generally similar to those of silica-supported catalysts; however, the reduction temperatures for the Ni–Cu–Sn and Ni–Sn oxides approach each other. The profiles for Ni3CuSn0.3/Al2O3 and Ni3CuSn0.3/TiO2 are similar, but different from that of Ni3CuSn0.3/CeO2. The reduction peak for Ni–Cu–Sn oxides merges with that of Ni–Sn oxides, implying greater incorporation of Sn into the Ni–Cu oxides. For Ni3CuSn0.3/MgO, in addition to the peaks typical for Ni3CuSn0.3, a broad peak occurs between 460 and 750 °C. This peak is likely associated with the reduction of NiO-MgO solid solutions,39 which consume part of the nickel oxides and, as a result, lead to smaller reduction peaks for the Ni–Cu, Ni–Cu–Sn, and Ni–Sn mixed oxides.

Figure 6.

Figure 6

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(a) H2-TPR profiles and (b) XRD patterns of metal oxide-supported catalysts.

Figure 6b presents the XRD patterns of the reduced catalysts. The characteristic diffraction peaks of the support materials are clearly identified for each catalyst (Al2O3: PDF#10–0425; MgO: PDF#45–0946; CeO2: PDF#43–1002; TiO2: PDF#21–1272). Nevertheless, the diffraction peaks of TiO2 in Ni3CuSn0.3/TiO2 are shifted by about 0.2° toward higher angles compared to the standard TiO2 reference, suggesting lattice contraction caused by metal incorporation into the TiO2 lattice.40,41 All catalysts exhibit the three characteristic diffraction peaks (2θ = 44.3, 51.6, and 75.7°) of unsupported Ni3CuSn0.3, as indicated by the dashed lines. Particularly, the Ni3CuSn0.3 peaks for Ni3CuSn0.3/Al2O3 and Ni3CuSn0.3/MgO are shifted to lower angles, indicating greater incorporation of Sn into the Ni–Cu oxide structure. According to the H2-TPR analysis, the Ni3CuSn0.3 peaks for Ni3CuSn0.3/TiO2 would also be expected to shift to lower angles; however, no such shift is observed. This phenomenon is probably owing to the incorporation of certain metals into the TiO2 lattice, which alters the peak position of Ni3CuSn0.3 due to the shift of TiO2 planes to higher angles. For Ni3CuSn0.3/Al2O3, a diffraction peak corresponding to quasi-Ni3Sn alloys is observed. For Ni3CuSn0.3/MgO, the peak of metallic Ni is detected, which can be attributed to the reduction of NiO-MgO solid solutions.

Figure 7 shows the micromorphology, metal particle size distribution, and elemental distribution of the metal oxide-supported Ni3CuSn0.3 catalysts. The black spots observed in the HRTEM images are attributed to metal particles, which are homogeneously distributed on each support, as confirmed by the elemental distribution maps of Ni, Cu, and Sn. For Ni3CuSn0.3/Al2O3, Ni3CuSn0.3/MgO, Ni3CuSn0.3/CeO2, and Ni3CuSn0.3/TiO2, the average metal particle sizes are 24.6, 10.1, 36.5, and 11.2 nm, respectively. Despite CeO2 and MgO having the highest and lowest specific surface areas among the metal oxide supports, the resulting catalysts exhibit the largest and smallest average metal particle sizes, reflecting the influence of metal–support interactions on metal particle size. In addition, lattice spacings of 0.177, 0.205, 0.206, 0.213, and 0.228 nm are observed, which do not match those of Ni, Cu, or Ni3Sn, suggesting the formation of Ni–Cu–Sn alloys.

Figure 7.

Figure 7

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Representative HRTEM, lattice fringe, metal particle size distribution, and elemental mapping images of (a1-a5) Ni3CuSn0.3/Al2O3, (b1-b5) Ni3CuSn0.3/MgO, (c1-c5) Ni3CuSn0.3/CeO2, and (d1-d5) Ni3CuSn0.3/TiO2.

Figure 8 presents the XPS spectra of Ni 2p, Cu 2p, Sn 3d, Al 2p, Mg 1s, and Ti 2p for the metal oxide-supported catalysts. The XPS spectra of Ni 2p, Cu 2p, and Sn 3d (Figure 8a-c) exhibit clear doublet structures, i.e., 2p1/2 and 2p3/2 for Ni 2p and Cu 2p, and 3d3/2 and 3d5/2 for Sn 3d. In the Ni 2p spectra, both the Ni 2p3/2 (850–868 eV) and Ni 2p1/2 (868–885 eV) regions can be deconvoluted into three peaks, corresponding to Ni0, Ni2+, and satellite peaks, respectively.42 In the Cu 2p spectra, only a single peak is identified in both the Cu 2p3/2 (928–940 eV) or Cu 2p1/2 (948–958 eV) regions, which belongs to Cu0.43 In the Sn 3d spectra, the Sn 3d5/2 (482–490 eV) and Sn 3d3/2 (491–498 eV) regions can be deconvoluted into two peaks, attributed to Sn0 and Sn2+/Sn4+, respectively.44 The dashed lines indicate the reference binding energies (BEs) for Ni0 2p3/2 (852.8 eV), Cu0 2p3/2 (932.4 eV), and Sn0 3d5/2 (484.8 eV).45 Due to the partial overlap of the Ni 2p1/2 and Ce 3d5/2 XPS peaks, the combined spectrum of Ni 2p and Ce 3d for Ni3CuSn0.3/CeO2 is provided in Figure S3. For the Ni3CuSn0.3 catalysts supported on Al2O3, MgO, CeO2, and TiO2, the BEs for Ni0 2p3/2 are 852.2, 852.2, 852.1, and 851.6 eV, respectively (Figures 8a and S3). The corresponding Cu0 2p3/2 BEs are 932.3, 933.3, 932.0, and 931.7 eV (Figure 8b), while the Sn0 3d5/2 BEs are 484.6, 484.5, 484.6, and 484.0 eV, respectively (Figure 8c). The Ni0 2p3/2, Cu0 2p3/2 and Sn0 3d5/2 peaks for Ni3CuSn0.3/Al2O3, Ni3CuSn0.3/CeO2 and Ni3CuSn0.3/TiO2 are shifted to lower BEs compared to the reference levels, implying electron-rich features of Ni, Cu and Sn atoms in these catalysts. In contrast, for Ni3CuSn0.3/MgO, the Ni0 2p3/2 and Sn0 3d5/2 peaks shift to lower BEs, while the Cu0 2p3/2 peak shifts toward a higher BE.

Figure 8.

Figure 8

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XPS spectra of (a) Ni 2p, (b) Cu 2p, (c) Sn 3d, (d) Al 2p, (e) Mg 1s, and (f) Ti 2p of metal oxide-supported Ni3CuSn0.3 catalysts.

Regarding the support materials, the Al 2p BE for Ni3CuSn0.3/Al2O3 is 74.6 eV (Figure 8d), which is higher than the reference level of 74.3 eV.46 Similarly, the Mg 1s BE for Ni3CuSn0.3/MgO is 1306.2 eV (Figure 8e), exceeding the reference level of 1303.2 eV.47 Based on the analysis of the Ni, Cu and Sn metals along with the support materials, it is inferred that for Ni3CuSn0.3/Al2O3, electron transfer occurs from Al2O3 to the Ni, Cu and Sn metals. In contrast, for Ni3CuSn0.3/MgO, electron transfer takes place from both Cu and MgO to the Ni and Sn metals. Such electron transfer phenomena involving Al2O3 and MgO have been documented in previous studies, including reports of electron transfer from Al2O3 to Au48 and from MgO to Cu.49 For Ni3CuSn0.3/TiO2, both Ti4+ and Ti3+ chemical states are detected (Figure 8f). This observation is in accordance with the XRD analysis, which indicates that the metals are doped into the TiO2 lattice, potentially leading to the formation of oxygen vacancies and structural defects.41 In addition, the Ti4+ 2p1/2 and Ti4+ 2p3/2 BEs of 464.2 and 458.4 eV, respectively, are 0.2 eV lower than the reference values,50 while the Ti3+ 2p1/2 BE of 460.6 eV is 0.4 eV higher. This suggests electron transfer from Ti3+ to Ni, Cu, and Sn. Likewise, for Ni3CuSn0.3/CeO2, both Ce4+ and Ce3+ are observed (Figure S3). The Ce3+ BEs (905.1, 900.3, 886.7, and 882.1 eV) are higher than the corresponding reference values (903.4, 899.1, 885.2, and 880.9 eV),51 implying electron transfer from Ce3+ to Ni, Cu, and Sn. Comparable electron transfer from Ti3+ or Ce3+ to metal atoms has also been reported for other catalysts, e.g., Au/TiO2,52 Pd/TiO2,53 Au/CeO2,54 and Ni–Cu/CeO2.55 In summary, the XPS analysis demonstrates electron transfer from the metal oxide supports to the Ni, Cu, and Sn metals. The degree of electron enrichment in Ni follows the sequence: Ni3CuSn0.3/MgO = Ni3CuSn0.3/Al2O3 < Ni3CuSn0.3/CeO2 < Ni3CuSn0.3/TiO2.

Figure 9 shows the phenylacetylene conversion and styrene selectivity for the four metal oxide-supported Ni3CuSn0.3 catalysts. For Ni3CuSn0.3/Al2O3, Ni3CuSn0.3/MgO, Ni3CuSn0.3/CeO2 and Ni3CuSn0.3/TiO2, the time needed for complete phenylacetylene conversion is 200, 210, 160, and 660 min (Figure 9a), respectively, while the initial reaction rates are calculated as 1.7, 1.6, 2.1, and 0.5 mmol/(g·min), respectively. Accordingly, the apparent activity increases in the order Ni3CuSn0.3/TiO2 < Ni3CuSn0.3/MgO < Ni3CuSn0.3/Al2O3 < Ni3CuSn0.3/CeO2. Ni3CuSn0.3/TiO2 exhibits significantly lower activity, likely due to the blockage of many metal particles within the pores of TiO2, as revealed by the preceding pore structure analysis. These occluded particles are hardly accessible to reactants, resulting in a great reduction in active sites. The catalytic activity of Ni3CuSn0.3/CeO2 is higher than that of Ni3CuSn0.3/Al2O3 and Ni3CuSn0.3/MgO, possibly owing to the lower degree of Sn incorporation into the Ni–Cu alloys in Ni3CuSn0.3/CeO2. For the same reason, the activity of Ni3CuSn0.3/MgO is slightly lower than that of Ni3CuSn0.3/Al2O3, as the former possesses a higher degree of Sn doping. This finding aligns with observations for silica-supported Ni3CuSn0.3 catalysts.

Figure 9.

Figure 9

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(a) Phenylacetylene conversion vs reaction time, and (b) styrene selectivity vs phenylacetylene conversion obtained for metal oxide-supported Ni3CuSn0.3 catalysts.

With regard to styrene selectivity, the catalysts are ranked in the order Ni3CuSn0.3/MgO < Ni3CuSn0.3/CeO2 < Ni3CuSn0.3/TiO2 < Ni3CuSn0.3/Al2O3 (Figure 9b). Their styrene selectivities at complete phenylacetylene conversion are 92.4%, 93.1%, 93.2%, and 94.1%, respectively, corresponding to styrene yields of 91.6%, 92.3%, 92.4%, and 93.5%. Apart from Ni3CuSn0.3/Al2O3, the order of selectivity corresponds to the degree of electron enrichment in Ni, illustrating the influence of electronic effects. This is reasonable, as it is well established that electron-rich metals can inhibit the adsorption of styrene, thereby reducing its subsequent hydrogenation.56,57 The high selectivity for Ni3CuSn0.3/Al2O3 is probably associated with the geometric effect. As indicated by the XRD analysis, Ni3CuSn0.3/Al2O3 clearly contains quasi-Ni3Sn alloy particles, which may promote active-site isolation and consequently enhance styrene selectivity. The geometric effect could be investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy. Unfortunately, we currently lack access to such equipment.

3.3. Solvent-Free Ball-Milling-Derived Ni3CuSn0.3/Al2O3 Catalyst

Among the seven supported Ni3CuSn0.3 catalysts studied in this work, Ni3CuSn0.3/Al2O3 exhibits the highest styrene selectivity (94.1%) and yield (93.5%) at complete phenylacetylene conversion. Although its hydrogenation activity is lower than that of the silica-supported catalysts, the stronger metal–support interaction means that Ni3CuSn0.3/Al2O3 may provide better long-term stability. While the activity of Ni3CuSn0.3/CeO2 is slightly higher than that of Ni3CuSn0.3/Al2O3, Al2O3 is more cost-effective and widely available compared to CeO2. Therefore, Ni3CuSn0.3/Al2O3 is chosen to assess the solvent-free ball milling preparation method. For clarity, the ball-milling-derived catalyst is denoted as Ni3CuSn0.3/Al2O3(m).

Ni3CuSn0.3/Al2O3(m) shows a similar H2-TPR profile (Figure 10a) and XRD pattern (Figure 10b) to those of the wet impregnation-derived Ni3CuSn0.3/Al2O3. The diffraction peaks assigned to Ni3CuSn0.3 shift slightly toward lower angles compared to the reference peaks (marked by dashed lines), indicating enhanced integration of Sn into the Ni–Cu alloys. In addition, a quasi-Ni3Sn phase is weakly detected. However, Ni3CuSn0.3/Al2O3(m) has much smaller metal particles, with an average size of 10.9 nm (Figure 10c), compared to 24.6 nm for Ni3CuSn0.3/Al2O3. The Ni, Cu, and Sn elements are uniformly distributed on Al2O3 (Figure 10d), reflecting good dispersion of the metal particles.

Figure 10.

Figure 10

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(a) H2-TPR profile, (b) XRD pattern, (c) HRTEM image, (d) elemental mapping images, and (e) phenylacetylene conversion and styrene selectivity vs reaction time for ball-milling-derived Ni3CuSn0.3/Al2O3(m).

Compared to the wet impregnation-derived Ni3CuSn0.3/Al2O3, the ball-milling-derived Ni3CuSn0.3/Al2O3(m) exhibits significantly increased catalytic performance (Figure 9 vs Figure 10e). Its initial hydrogenation rate is 4.5 mmol/(g·min), which is 2.6 times higher than that of Ni3CuSn0.3/Al2O3. Accordingly, the time required for complete phenylacetylene conversion is shortened to 80 min. This improved activity can be attributed to the smaller metal particle size. In addition, styrene selectivity and yield at complete phenylacetylene conversion increase to 95.0% and 94.9%, respectively.

Ni3CuSn0.3/Al2O3(m) was further tested over five consecutive cycles to evaluate its reusability. The reaction condition remained the same as described above, except the reaction time was intentionally limited to 60 min to avoid complete phenylacetylene conversion, which could obscure potential catalyst deactivation. After each cycle, the catalyst was separated from the reaction mixture by centrifugation, washed with ethanol, and reused. As presented in Figure S4, both phenylacetylene conversion and styrene selectivity remain nearly constant, with average values of 81.4% and 95.7%, respectively, which demonstrates good stability. Moreover, its crystal phase structure and micromorphology are well preserved after 5 cycles (Figure S5). The average metal particle size of the used catalyst (10.7 nm) is almost identical to that of the fresh sample, and the Ni, Cu, and Sn contents are measured to be 19.7, 7.2, and 3.8 wt %, respectively, indicating no metal leaching. In view of its scalable preparation and cost-effectiveness, the solvent-free ball-milling-derived Ni3CuSn0.3/Al2O3 holds promise for practical industrial applications.

4. Conclusions

A series of Ni3CuSn0.3 catalysts supported on silica (SiO2(1), SiO2(2), and SBA-15) and metal oxides (Al2O3, MgO, CeO2, and TiO2) were prepared by wet impregnation. Among the silica-supported catalysts, Ni3CuSn0.3/SBA-15 possessed the highest specific surface area and the smallest average metal particle size, resulting in the highest activity in phenylacetylene hydrogenation as anticipated. However, Ni3CuSn0.3/SiO2(1) displayed higher activity than Ni3CuSn0.3/SiO2(2), despite the latter having smaller metal particles. This behavior is attributed to the higher degree of Sn incorporation into the Ni–Cu solid solution alloys in Ni3CuSn0.3/SiO2(2). For the silica-supported catalysts, the initial hydrogenation rates ranged from 4.7 to 7.0 mmol/(g·min) at 60 °C and 0.5 MPa, while the styrene selectivity at complete phenylacetylene conversion varied between 91.9% and 92.8%. In comparison, the metal oxide-supported catalysts showed lower activity, with initial rates deceasing to 0.5–2.1 mmol/(g·min), but demonstrated higher styrene selectivity, ranging from 92.4 to 94.1%. The hydrogenation activities of metal oxide-supported catalysts were strongly influenced by the degree of Sn incorporation into Ni–Cu alloys, which was governed by metal–support interactions. For instance, Ni3CuSn0.3/CeO2, with a low degree of Sn incorporation, exhibited high activity, whereas Ni3CuSn0.3/MgO, characterized by a high degree of Sn incorporation, displayed lower activity. The selectivity of metal oxide-supported catalysts was affected by electronic and geometric effects. The presence of electron-rich Ni and quasi-Ni3Sn alloy particles made Ni3CuSn0.3/Al2O3 the catalyst with the highest styrene selectivity. When compared to its wet impregnation-derived counterpart, the solvent-free ball-milling-derived Ni3CuSn0.3/Al2O3 demonstrated enhanced performance, with the initial rate increasing from 1.7 to 4.5 mmol/(g·min) and styrene selectivity at complete phenylacetylene conversion improving from 94.1% to 95.0%. Furthermore, it exhibited good reusability, maintaining its properties and performance over five consecutive reaction cycles. To assess its potential for practical applications, future studies will investigate the performance of pelletized Ni3CuSn0.3/Al2O3 during long-term continuous operation in a fixed-bed reactor.

Acknowledgments

Financial support from the National Natural Science Foundation of China (21978093 and22278143) is gratefully acknowledged.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.5c01829.

  • HRTEM and EDS mapping images; metal particle size distribution; XPS spectra; reusability test results; and XRD pattern (PDF)

The authors declare no competing financial interest.

Supplementary Material

ao5c01829_si_001.pdf (530.1KB, pdf)

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