Next Article in Journal
Advances in Liquid-Phase Synthesis: Monitoring of Kinetics for Platinum Nanoparticles Formation, and Pt/C Electrocatalysts with Monodispersive Nanoparticles for Oxygen Reduction
Next Article in Special Issue
Zirconium Phosphates and Phosphonates: Applications in Catalysis
Previous Article in Journal
Synthesis of Tetrahydrocarbazole-Tethered Triazoles as Compounds Targeting Telomerase in Human Breast Cancer Cells
Previous Article in Special Issue
Bisphenol F Synthesis from Formaldehyde and Phenol over Zeolite Y Extrudate Catalysts in a Catalyst Basket Reactor and a Fixed-Bed Reactor
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Catalysts
Volume 14
Issue 10
10.3390/catal14100727
catalysts-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

The Effects of Support Specific Surface Area and Active Metal on the Performance of Biphenyl Selective Hydrogenation to Cyclohexylbenzene

by
Jie Fan
1,
Wei Li
1,
Jingyi Yang
2,
Tao Yang
1,
Zhongyi Liu
1,3,* and
Meng Zhang
1,*
1
College of Chemistry, Zhengzhou University, Zhengzhou 450001, China
2
School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, China
3
State Key Laboratory of Coking Coal Resources Green Exploitation, Zhengzhou University, Zhengzhou 450001, China
*
Authors to whom correspondence should be addressed.
Catalysts 2024, 14(10), 727; https://doi.org/10.3390/catal14100727
Submission received: 26 September 2024 / Revised: 14 October 2024 / Accepted: 15 October 2024 / Published: 17 October 2024
(This article belongs to the Special Issue Feature Papers in "Industrial Catalysis" Section)
Browse Figures
Versions Notes

Abstract

:
With the rapid development of modern society, the consumption of fossil fuels during the industrial production process produces a significant amount of carcinogens. Converting the highly toxic biphenyl (BP) to the valuable product cyclohexylbenzene (CHB) can decrease the emission of carcinogenic aromatic hydrocarbons. In this study, we prepared a series of 20%Ni/SiO2 catalysts with different specific surface areas (SSAs) using the over-volume impregnation method, as well as 20%M/SiO2 (M = Fe, Cu, Co, and Ni) catalysts to highlight the effects of support SSAs and active metal on the performance of BP selective hydrogenation to CHB. The catalysts were characterized by XRD, N2 physisorption, TEM, and H2-TPR, which demonstrated that a high SSA would be helpful for the dispersion of the active metal. The evaluation results revealed that 20%Ni/SiO2-300 exhibited excellent activity and stability in the selective hydrogenation of BP to CHB (BP conversion: 99.6%, CHB yield: 99.3% at the conditions of 200 °C, 3 MPa, 4 h and isopropanol as the solvent) among the catalysts with different SSAs, which was also superior to the performance over the catalysts with other transition metals as the active sites. The structure–activity relationship of the employed catalysts for the selective hydrogenation of BP to CHB was also discussed.

1. Introduction

With the rapid development of the modern economic society, the excessive consumption of fossil fuels, mainly coal, oil, and natural gas, is remarkably increasing [1]. The process of industrial production produces large amounts of carcinogens [2]. Among these carcinogens, aromatic compounds are the most diverse and toxic [3]. Therefore, it is of great importance to reduce the emissions of aromatic hydrocarbons [4,5,6].
Hydrogenation is one of the most commonly used methods to reduce the emission of aromatic organic compounds during the industrial production processes [7,8,9]. Biphenyl (BP) is a common aromatic compound that exists in coal tar, crude oil, and natural gas. It has remarkable toxic effects on the nervous system, digestive system, and kidneys [10]. Although it is relatively difficult to carry out hydrogenation, the hydrogenation products, cyclohexylbenzene (CHB) and bicyclohexane (BCH), have high added values [10,11,12]. CHB serves not only as a buffering solution for lithium-ion batteries but also as a promising raw material for producing phenol and cyclohexanone [13,14]. BCH is an important high-boiling solvent and penetrant [15].
At present, the active components for BP hydrogenation are mainly noble metals [16,17], but the disadvantages of high cost and uncontrollable selectivity hinder their large-scale application. Many studies have explored various non-noble metals as active centers for catalyzing BP hydrogenation, among which the application of Ni is the most extensive [18,19,20]. Lu et al. [8] prepared an Al-Ni-based catalyst that achieved a 100% conversion rate of BP and a 99.4% selectivity for CHB under the conditions of 70 °C, 1 MPa, and 4 h. Olivas et al. [11] prepared a NiMoWS catalyst that achieved a 99% conversion rate of BP and a 52% selectivity for CHB under the reaction conditions of 300 °C, 5.5 MPa, and 4 h.
The performance of the catalytic hydrogenation reactions is closely related to the structural properties of the support [21,22,23]. Chernova et al. [23] studied the effects of support types (SBA-15, SiO2, and Al2O3) and specific surface areas (SSAs) on the performance of BP hydrogenation reactions. The results showed that a larger SSA can provide more active sites, thereby contributing to the progress of the reaction. However, when the SSA is too large, it leads to the excessive diffusion and adsorption ability of reactant molecules on the surface, which increases the interaction between reactant molecules, and slows down the reaction rate as well as the selectivity.
Moreover, the pore structure of catalyst supports has a significant impact on hydrogenation reactions [21,24]. Hongmanorom et al. [25] found that larger pores facilitate the entry of reactant molecules into the active sites, while smaller pores can limit product diffusion and improve selectivity. The morphology of supported catalysts has an important impact on hydrogenation reactions [26,27,28]. Some studies have shown that supports with specific morphologies can enhance the activity and selectivity of catalysts, thereby promoting hydrogenation reactions. Shi et al. [29] found that catalysts with a large SSA and mesoporous structure are beneficial to both dibenzyl toluene (DBT) hydrogenation and perhydrodibenzyl toluene (H18-DBT) dehydrogenation activity.
Furthermore, active metals also have significant effects on the hydrogenation performance [10,17,30]. Tamizhdurai et al. [31] found that the performance of Pt-based catalysts was superior to Ru-based and Ni-based catalysts in the hydrogenation of dicyclopentadiene (DCPD) to tetrahydrodicyclopentadiene (THDCPD). O’Driscoll et al. [32] synthesized single-metal catalysts using the wet impregnation method and prepared Pt-, Pd-, Cu- and Ni-based catalysts for the selective hydrogenation of furfural to furfuryl alcohol. The results indicated that Pd-based catalysts have the best performance and exhibit higher selectivity compared to other metals.
In the current investigation, we prepared a series of 20%Ni/SiO2 catalysts with different SSAs, as well as 20%M/SiO2 (M = Fe, Cu, Co, and Ni) catalysts with different active metals using the over-volume impregnation method. A series of characterization techniques, including XRD, N2 physisorption, TEM, and H2-TPR, were used to analyze the physicochemical properties of the catalysts. In combination with the evaluation results, the influences of the support SSA and active metals on the selective hydrogenation performance of BP were explored.

2. Results and Discussion

2.1. Characterization of Ni-Based Catalysts with Different SSAs

Figure 1 shows the XRD patterns of the calcined 20%Ni/SiO2 catalysts with different SSAs. The broad peaks observed at 2θ = 22° for all catalysts are attributed to the amorphous structure of the silica support. Additionally, all the catalysts displayed diffraction peaks at 2θ = 37.2°, 43.2°, 62.9°, 75.5° and 79.5°, corresponding to the (111), (002), (022), (113), and (222) planes of NiO (PDF#96-101-0094), respectively [33]. No other impurity peaks can be seen in Figure 1, indicating that Ni(NO3)2 has been completely reduced decomposed and converted into NiO [34].
Figure 2 shows the H2-temperature programmed reduction (H2-TPR) profiles of 20%Ni/SiO2 catalysts with different SSAs, and the reduction behavior of Ni2+ in different samples was analyzed. Figure 2 shows that the four catalyst samples display a broad reduction peak at 350–370 °C, attributed to the reduction of NiO to metallic Ni [35]. The reduction temperature varies with the specific surface area of SiO2. As observed, a moderate increase in specific surface area causes the peak position to shift towards a high temperature, gradually increasing from 355 °C to 366 °C. The peak areas are not significantly different, indicating that the precursor oxides of catalysts with different SSAs consume approximately the same amount of H2 during the reduction process. Additionally, it can be observed that the peak position of the sample 20%Ni/SiO2-400 shifts towards a low temperature, reaching 352 °C, and the peak area is slightly larger compared to other samples. It indicates that the catalyst with a larger specific surface area consumes more H2.
Figure 3 shows the XRD patterns of 20%Ni/SiO2 catalyst precursors with different SSAs after reduction. All catalysts display characteristic diffraction peaks at 2θ = 22°, corresponding to the amorphous structure of the silica support. In addition, all catalysts exhibit three Ni (PDF#96-901-2965) signal diffraction peaks at 2θ = 44.5°, 51.8°, and 76.4°, which correspond to the (111), (200), and (220) crystal planes [24], respectively. It is worth noting that no observable diffraction peaks related to NiO were found, indicating that NiO was completely reduced to Ni0 [36,37].
The N2 adsorption–desorption isotherms and pore size distribution of 20%Ni/SiO2 catalysts with different SSAs are shown in Figure 4a,b, respectively, to investigate the influence of supports with different SSAs on the structure of the catalyst samples.
It can be observed in Figure 4a that no hysteresis loop is present when the relative pressure P/P0 is less than 0.1. However, a distinct hysteresis loop appears when the relative pressures P/P0 exceed 0.8, indicating the presence of typical IV-type isotherms and the existence of mesoporous structures [38].
According to the results calculated using the BET model (Table 1), the SSAs of the samples gradually increase from 152 m2·g−1 to 229 m2·g−1, while the change in pore volume is not significant. The average pore size shows an initial increasing trend followed by a decrease. It is evident that the catalysts in this series have relatively large pore sizes, which facilitates the exposure of metal sites, thereby promoting the catalytic activity for the selective hydrogenation of BP.
Figure 5 shows the TEM images and the particle size distribution histograms of 20%Ni/SiO2 catalysts with different SSAs. From the images, it can be observed that small spherical particles around 20 nm are well dispersed on the surface of support. Notably, as the specific surface area of the support increases from 100 m2·g−1 to 400 m2·g−1, the size of Ni particles decreases from 23.3 nm to 19.8 nm, indicating that an increase in the specific surface area of the support leads to a more uniform dispersion of active metal components on the surface, resulting in smaller metal particles [39]. The Scherrer formula was used to calculate the size of metal particles of 20%Ni/SiO2 catalysts with different SSAs, and the calculation results are shown in Table 1.

2.2. Characterization of 20%M/SiO2 (M = Fe, Cu, Co, and Ni) Catalysts

Figure 6 shows the XRD patterns of 20%M/SiO2 (M = Cu, Co, Fe) catalyst precursors after calcination. The characteristic diffraction peaks corresponding to the crystal plane of metal oxides in these catalyst samples can be clearly observed from the patterns. For the CuO/SiO2 sample, four characteristic diffraction peaks of CuO (PDF#01-089-58987) can be observed. Strong, sharp diffraction peaks at 2θ = 35.5°, 38.7° and 38.9° are ascribed to the CuO (002), (111) and (220) planes, respectively, with a weaker peak at 2θ = 48.7° corresponding to the (−202) plane of CuO [40]. Seven peaks are assigned to Fe2O3 (PDF#01-073-2234) in the XRD pattern of the Fe2O3/SiO2 sample, which are centered at 2θ = 24.1°, 33.2°, 35.7°, 49.5°, 54.1°, 62.5° and 64.0° and correspond to the (012), (104), (110), (024), (116), (214)and (300) planes [41], respectively. For the Co3O4/SiO2 sample, two sharp diffraction peaks at 2θ = 31.2° and 65.2° are ascribed to the (220) and (440) planes of Co3O4 (PDF#00-001-1152), along with a strong peak at 2θ = 37.0° corresponding to the Co3O4 (311) plane [42]. As can be seen from Figure 6, Cu(NO3)2, Fe(NO3)3 and Co(NO3)2 have completely decomposed, resulting in the formation of CuO, Fe2O3 and Co3O4.
The H2-temperature programmed reduction (H2-TPR) curves of 20%M/SiO2 (M = Cu, Co, Fe) catalysts are shown in Figure 7, demonstrating the reducibility and redox behavior of different samples. The H2-TPR profile of 20%Cu/SiO2 exhibits a peak at 281 °C, assigned to the reduction of Cu2+ to Cu+ [43,44]. A subsequent peak at 334 °C is attributed to the reduction of Cu+ to Cu0 [45]. This indicates that CuO can be completely reduced to Cu0 when the reduction temperature reaches 400 °C. The H2-TPR profile of 20%FeO/SiO2 shows a broad peak at 359 °C, attributed to the reduction of Fe3+ to Fe2+ [46]. And a slightly lower broad peak can also be observed at 672 °C, attributed to the reduction of Fe2+ to Fe0 [41]. This suggests that Fe2O3 cannot be fully reduced to Fe0 at a reduction temperature of 550 °C. The H2-TPR profile of 20%Co/SiO2 exhibits a peak at 296 °C, indicating the reduction of Co3+ to Co2+ [47]. Another peak at 348 °C corresponds to the reduction of Co2+ to Co0 [48]. Thus, when the reduction temperature reaches 550 °C, CoO can be completely reduced to Co0 [49]. These results are consistent with the XRD data in Figure 6.
The XRD patterns of 20%M/SiO2 (M = Cu, Co, Fe) catalysts after reduction are shown in Figure 8. All samples exhibit SiO2 characteristic diffraction peaks at 2θ = 22°. Three distinct characteristic diffraction peaks of Cu (PDF#96-901-2955) can be observed in the XRD pattern of the 20%Cu/SiO2 sample. A strong peak at 2θ = 43.4° corresponds to the Cu (111) crystal plane [45], while two weak peaks at 2θ = 50.6 and 74.3° correspond to the Cu (002) and (022) crystal planes [49]. Notably, no impurity peaks are observed, indicating that CuO has been completely reduced to Cu0 [50].
Six diffraction peaks of Co (PDF#01-089-7094) can be observed in the XRD pattern of the 20%Co/SiO2 sample. A strong diffraction peak at 2θ = 47.4° ascribed to the Co (101) crystal plane [51,52], and five weak peaks at 2θ = 41.6°, 44.5°, 62.5°, 75.8°, and 84.1° correspond to the Co (100), (002), (102), (110), and (103) crystal planes [53]. In the 20%Fe/SiO2 sample, three Fe (PDF#96-900-65) signal diffraction peaks at 2θ = 44.7°, 65.1°, and 82.4° correspond to the (011), (002), and (112) crystal planes [54]. Furthermore, a distinct diffraction peak related to Fe2O3 can be observed at 2θ = 35.7°, indicating that even after reduction at 550 °C for 3 h, Fe2O3 has not been completely reduced to Fe0 [55]. These findings are consistent with the results of the H2-TPR results in Figure 7.
N2 adsorption–desorption isotherms and pore size distributions of 20%M/SiO2 (M = Cu, Co, Fe) catalysts are depicted in Figure 9a,b, investigating the structural influence of different active metals on the catalyst samples. It can be observed from the figures that when the relative pressure P/P0 is less than 0.1, no hysteresis curve is evident. However, a distinct hysteresis curve can be observed at relative pressures P/P0 = 0.8 to 1.0, indicating that these three samples exhibit mesoporous materials [30].
According to Figure 9a and the BET model calculation results (Table 2), the specific surface areas of this series of catalysts show minimal variation. The SSA of all three samples is around 210 m2·g−1. Additionally, based on Figure 9b and Table 2, it is evident that the pore sizes and pore volumes of these catalysts are also quite similar. When compared with the previous 20%Ni/SiO2-300 catalyst, the differences in specific surface area and pore size are not significant.

2.3. 20% Ni/SiO2 Catalysts with Different SSAs for BP Hydrogenation

The selective hydrogenation of BP was conducted in a high-pressure autoclave reactor under a hydrogen pressure of 2 MPa and temperatures of 200 °C employing an online continuous sampling technique (sampling every 60 min). The experimental results are shown in Figure 10.
From Figure 10, it can be observed that three catalyst samples (20%Ni/SiO2-100/200/400) exhibit similar trends; as the reaction time increases, the conversion rate of BP increases, while the selectivity towards CHB decreases. The 20%Ni/SiO2-300 catalyst had already achieved BP conversion and CHB selectivity close to 100% when the reaction time was 60 min, and there was little change with the extension of time. Overall, the performance of all four catalysts was satisfactory, while the 20%Ni/SiO2-300 sample demonstrated superior catalytic performance. At 240 min, the BP conversion rate reached 99.6% and the yield of CHB reached 99.3%. Therefore, it is evident that the SSA of the SiO2 support has a significant impact on the selective hydrogenation performance of BP to CHB. It is believed that when the SSA of the SiO2 support is small, the Ni particles are larger, with a small amount of aggregation and fewer active sites every unit, whereas a larger SSA can lead to excessive hydrogenation, resulting in a decreased CHB yield. Therefore, for subsequent preparations of supported metal catalysts with different types of active metals, 20%Ni/SiO2-300 was chosen as the preferred support.

2.4. 20% M/SiO2 (M = Cu, Co, Fe) Catalysts for BP Hydrogenation

The hydrogenation activity of 20%M/SiO2 (M = Cu, Co, Fe) catalysts under the same reaction conditions was evaluated at the same time, and the activity results are shown in Figure 11.
From Figure 11, it can be observed that 20%Co/SiO2, 20%Fe/SiO2 and 20%Cu/SiO2 catalysts exhibited conversions of only 11.9%, 2.5% and 43%, respectively, at 240 min, achieving a CHB yield of 11.64%, 2.4% and 42.5% at 240 min, respectively. While the Cu-based catalyst showed gradual improvement in catalytic hydrogenation activity over time, the 20%Ni/SiO2 catalyst achieved higher conversions of 99.6% with a CHB yield of 99.3% at 240 min under a hydrogen pressure of 2 MPa and temperatures of 200 °C. Therefore, it can be concluded that the Ni-based catalyst is more suitable for this reaction due to its higher activity in the selective hydrogenation of BP to CHB.

2.5. Cycle Stability of 20% Ni/SiO2-300

Figure 12 shows the cyclic stability of selective hydrogenation of BP using the 20%Ni/SiO2-300 sample under the reaction conditions of 120 °C, 2 MPa and 80 min. It can be observed that after the catalyst was used for five cycles, the conversion rate of BP slightly decreased, while the selectivity of CHB remained almost unchanged. Furthermore, we compared the 20%Ni/SiO2-300 sample with other catalysts that are similarly used for BP hydrogenation, as shown in Table S1. This further proves that the 20% Ni/SiO2-300 sample has high stability and performs well in repeated use under mild reaction conditions.

3. Materials and Methods

3.1. Materials

Fumed silica (SBET = 100 m2g−1, 200 m2g−1, 300 m2g−1, and 400 m2g−1), Ni(NO3)2·6H2O, Co(NO3)2·6H2O, Fe(NO3)3·9H2O and Cu(NO3)2·3H2O were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., (Shanghai, China). Biphenyl was purchased from Shanghai McLean Biochemical Technology Co., Ltd., (Shanghai, China). Isopropanol was purchased from Tianjin Fengchuan Chemical Reagent Technology Co., Ltd., (Tianjin, China) All reagents were used directly without further purification.

3.2. Catalyst Preparation

3.2.1. Preparation of 20%Ni/SiO2 Catalysts

The employed catalysts were prepared using the over-volume impregnation method. A specific amount of SiO2 support was weighed accurately, and a solution of the corresponding concentration was prepared based on the stoichiometric ratio, with a target Ni loading of 20 wt%. The obtained samples were dried at 60 °C for 4 h. After drying, the samples were ground into powder and calcined in a muffle furnace at 350 °C for 3 h. Finally, the calcined catalyst was reduced at 550 °C in a 10 vol%H2/N2 atmosphere for 3 h to obtain the reduced catalyst. The catalysts were simplified as 20%Ni/SiO2-100, 20%Ni/SiO2-200, 20%Ni/SiO2-300, and 20%Ni/SiO2-400.

3.2.2. Preparation of 20%M/SiO2 Catalysts

The preparation processes of 20%M/SiO2 were the same as the description in Section 3.2.1, where Ni(NO3)2·6H2O, Co(NO3)2·6H2O, Fe(NO3)3·9H2O and Cu(NO3)2·3H2O were the precursors and the fumed silica (SBET = 300 m2g−1) was the support. The prepared catalysts were denoted as 20%Ni/SiO2, 20%Fe/SiO2, 20%Co/SiO2, and 20%Cu/SiO2.

4. Conclusions

In summary, this study synthesized a series of 20%Ni/SiO2 catalysts with varied SSAs using the over-volume impregnation method and investigated their performance in the selective hydrogenation of BP to produce CHB. The characterization results indicated that the SSA of the supports significantly influenced the composition, structure, and surface morphology of the catalysts. The 20%Ni/SiO2-300 catalyst, with an optimal SSA, exhibited excellent activity in the hydrogenation of BP to CHB. Under the reaction conditions of 200 °C and 3 MPa H2 pressure, BP conversion reached 99.6% with a CHB yield of 99.3% within 240 min. This was attributed to the balanced dispersion of active sites facilitated by the moderate SSA of the support. Conversely, smaller SSAs hinder active site dispersion, while larger SSAs lead to excessive hydrogenation, both resulting in the decreased yield of the target product.
Additionally, we prepared and evaluated four different single metal-loaded catalysts (20%Co/SiO2, 20%Ni/SiO2, 20%Fe/SiO2, and 20%Cu/SiO2) for BP hydrogenation. Among these, the 20%Ni/SiO2 exhibited exceptional activity, achieving BP conversion of 99.6% and a CHB yield of 99.3%. This study provides valuable insights into the design of supported catalysts for the selective hydrogenation of BP.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/catal14100727/s1, Table S1. Cycle stability over the available catalysts for BP hydrogenation. Ref. [56] is cited in Supplementary Materials.

Author Contributions

Conceptualization, M.Z.; methodology, W.L. and J.Y.; validation, J.F.; formal analysis, J.F. and W.L.; investigation, W.L. and J.Y.; resources, Z.L.; writing—original draft preparation, J.F. and T.Y.; writing—review and editing, J.Y. and M.Z.; supervision, Z.L. and M.Z.; project administration, M.Z.; funding acquisition, Z.L. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Data Availability Statement

The data are contained in the article.

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Sharma, S.; Singh, P.; Bhardwaj, C.; Khandelwal, B.; Kumar, S. Investigations on combustion and emissions characteristics of aromatic fuel blends in a distributed combustor. Energy Fuels 2021, 35, 3150–3163. [Google Scholar] [CrossRef]
  2. Amirdivani, S.; Khorshidian, N.; Dana, M.G.; Mohammadi, R.; Mortazavian, A.M.; de Souza, S.L.Q.; Rocha, H.B.; Raices, R. Polycyclic aromatic hydrocarbons in milk and dairy products. Int. J. Dairy Technol. 2019, 72, 120–131. [Google Scholar] [CrossRef]
  3. Schifter, I.; Diaz, L.; Sanchez-Reyna, G.; Gonzalez-Macias, C.; Gonzalez, U.; Rodriguez, R. Influence of gasoline olefin and aromatic content on exhaust emissions of 15% ethanol blends. Fuel 2020, 265, 116950. [Google Scholar] [CrossRef]
  4. Stanislaus, A.; Marafi, A.; Rana, M.S. Recent advances in the science and technology of ultra low sulfur diesel (ULSD) production. Catal. Today 2010, 153, 1–68. [Google Scholar] [CrossRef]
  5. Lin, Y.-C.; Lee, W.-J.; Chen, C.-C.; Chen, C.-B. Saving energy and reducing emissions of both polycyclic aromatic hydrocarbons and particulate matter by adding bio-solution to emulsified diesel. Environ. Sci. Technol. 2006, 40, 5553–5559. [Google Scholar] [CrossRef]
  6. Song, Y.; Ding, X.; Li, F.; Zhang, D.; Zhao, X.; Wang, Y. A novel and green synthesis of methylcyclohexane diisocyanate: Reaction properties, deactivation and regeneration of Rh/γ-Al2O3 catalyst in benzene ring selective hydrogenation. Appl. Catal. A-Gen. 2023, 651, 119017. [Google Scholar] [CrossRef]
  7. Fahy, J.; Trimm, D.L.; Cookson, D.J. Four component catalysis for the hydroalkylation of benzene to cyclohexyl benzene. Appl. Catal. A-Gen. 2001, 211, 259–268. [Google Scholar] [CrossRef]
  8. Lu, L.; Rong, Z.; Du, W.; Ma, S.; Hu, S. Selective hydrogenation of single benzene ring in biphenyl catalyzed by skeletal Ni. ChemCatChem 2009, 1, 369–371. [Google Scholar] [CrossRef]
  9. Fu, H.; Zhang, H.; Yang, G.; Liu, J.; Xu, J.; Wang, P.; Zhao, N.; Zhu, L.; Chen, B.H. Highly dispersed rhodium atoms supported on defect-rich Co(OH)2 for the chemoselective hydrogenation of nitroarenes. New J. Chem. 2022, 46, 1158–1167. [Google Scholar] [CrossRef]
  10. Hiyoshi, N.; Rode, C.V.; Sato, O.; Shirai, M. Biphenyl hydrogenation over supported transition metal catalysts under supercritical carbon dioxide solvent. Appl. Catal. A-Gen. 2005, 288, 43–47. [Google Scholar] [CrossRef]
  11. Olivas, A.; Gaxiola, E.; Cruz-Reyes, J.; Alvarez-Amparan, M.A.; Valdez, R. Transition-metal influence (Fe, Cu) on the MoWS catalyst for biphenyl hydrogenation. Fuel Process. Technol. 2020, 204, 106410. [Google Scholar] [CrossRef]
  12. Yang, Y.; You, Y.; Wu, J.; Feng, J.; Zhang, Y. Phosphotungstic acid encapsulated in USY zeolite as catalysts for the synthesis of cyclohexylbenzene. J. Iran Chem. Soc. 2021, 18, 573–580. [Google Scholar] [CrossRef]
  13. Xu, M.Q.; Xing, L.D.; Li, W.S.; Zuo, X.X.; Shu, D.; Li, G.L. Application of cyclohexyl benzene as electrolyte additive for overcharge protection of lithium ion battery. J. Power Sources 2008, 184, 427–431. [Google Scholar] [CrossRef]
  14. Liu, L.; Zhao, J.; Liu, J. Relationship analysis of lithium battery over charge performance and CHB. Chin. J. Power Sources 2017, 41, 205–207. [Google Scholar]
  15. Li, W.; Zhao, Z.; Li, J.; Liu, Y.; Gao, B.; Li, X.; Zhang, M.; Liu, Z. Effects of Ni-loading on the performance of Ni/SiO2 catalysts for the highly selective hydrogenation of biphenyl to cyclohexylbenzene. ChemistrySelect 2021, 6, 3897–3902. [Google Scholar] [CrossRef]
  16. Kalenchuk, A.N.; Koklin, A.E.; Bogdan, V.I.; Kustov, L.M. Hydrogenation of biphenyl and isomeric terphenyls over a Pt-containing catalyst. Russ. Chem. Bull. 2017, 66, 1208–1212. [Google Scholar] [CrossRef]
  17. Yang, J.; Ma, J.-J.; Zhang, D.-M.; Xue, T.; Guan, Y.-J. Effect of organic moieties (phenyl, naphthalene, and biphenyl) in Zr-MIL-140 on the hydrogenation activity of Pd nanoparticles. Chin. Chem. Lett. 2016, 27, 1679–1682. [Google Scholar] [CrossRef]
  18. Baigildin, I.G.; Karakhanov, E.A.; Maximov, A.L.; Vutolkina, A.V. Biphenyl hydrogenation with syngas for hydrogen purification and transportation: Performance of dispersed catalytic systems based on transition metal sulfides. Pet. Chem. 2021, 61, 1131–1137. [Google Scholar] [CrossRef]
  19. Philippov, A.A.; Chibiryaev, A.M.; Martyanov, O.N. Catalyzed transfer hydrogenation by 2-propanol for highly selective PAHs reduction. Catal. Today 2021, 379, 15–22. [Google Scholar] [CrossRef]
  20. Nunez, S.; Montesinos-Castellanos, A.; Zepeda, T.A.; Los Reyes, J.A. Performance and S resistance of novel supported PdPt catalysts on Al2O3-TiO2 material in hydrogenation of biphenyl. Mater. Res. Innov. 2008, 12, 55–59. [Google Scholar] [CrossRef]
  21. Kondrateva, V.Y.; Martynenko, E.A.; Pimerzin, A.A.; Verevkin, S.P. Effect of support on catalytic properties of platinum-containing catalysts in hydrogenation of a biphenyl-diphenylmethane eutectic mixture. Russ. J. Appl. Chem. 2022, 95, 126–134. [Google Scholar] [CrossRef]
  22. Yang, J.; Gao, Y.; Fan, J.; Wang, J.; Yang, T.; Bing, Z.; Zhang, M.; Liu, Z. Boosting the selective hydrogenation of biphenyl to cyclohexylbenzene over bimetallic Ni-Ru/SiO2 catalyst via enhancing strong metal-support interaction. Appl. Surf. Sci. 2024, 660, 160012. [Google Scholar] [CrossRef]
  23. Chernova, M.M.; Minayev, P.P.; Martynenko, Y.A.; Pimerzin, A.A.; Yeremina, Y.V.; Verevkin, S.P.; Pimerzin, A.A. An effect of a support nature and active phase morphology on catalytic properties of Ni-containing catalysts in hydrogenation of biphenyl. Russ. J. Appl. Chem. 2018, 91, 1701–1710. [Google Scholar] [CrossRef]
  24. Yang, F.; Liu, D.; Zhao, Y.; Wang, H.; Han, J.; Ge, Q.; Zhu, X. Size dependence of vapor phase hydrodeoxygenation of m-Cresol on Ni/SiO2 catalysts. ACS Catal. 2018, 8, 1672–1682. [Google Scholar] [CrossRef]
  25. Hongmanorom, P.; Luengnaruemitchai, A.; Chollacoop, N.; Yoshimura, Y. Effect of the Pd/MCM-41 pore size on the catalytic activity and cis-trans selectivity for partial hydrogenation of canola biodiesel. Energy Fuels 2017, 31, 8202–8209. [Google Scholar] [CrossRef]
  26. Yang, Y.; Miao, C.; Wang, R.; Zhang, R.; Li, X.; Wang, J.; Wang, X.; Yao, J. Advances in morphology-controlled alumina and its supported Pd catalysts: Synthesis and applications. Chem. Soc. Rev. 2024, 53, 5014–5053. [Google Scholar] [CrossRef]
  27. Zhu, L.; Zheng, T.; Zheng, J.; Yu, C.; Zhang, N.; Zhou, Q.; Zhang, W.; Chen, B.H. Shape control of nickel crystals and catalytic hydrogenation performance of ruthenium-on-Ni crystals. Crystengcomm 2018, 20, 113–121. [Google Scholar] [CrossRef]
  28. Garcia-Perez, D.; Alvarez-Galvan, M.C.; Campos-Martin, J.M.; Fierro, J.L.G. Influence of the reduction temperature and the nature of the support on the performance of zirconia and alumina-supported Pt catalysts for n-dodecane hydroisomerization. Catalysts 2021, 11, 88. [Google Scholar] [CrossRef]
  29. Shi, L.; Zhou, Y.; Tan, X.; Qi, S.; Smith, K.J.; Yi, C.; Yang, B. The effects of alumina morphology and Pt electron property on reversible hydrogenation and dehydrogenation of dibenzyltoluene as a liquid organic hydrogen carrier. Int. J. Hydrogen Energy 2022, 47, 4704–4715. [Google Scholar] [CrossRef]
  30. Castano, P.; Zepeda, T.A.; Pawelec, B.; Makkee, M.; Fierro, J.L.G. Enhancement of biphenyl hydrogenation over gold catalysts supported on Fe-, Ce- and Ti-modified mesoporous silica (HMS). J. Catal. 2009, 267, 30–39. [Google Scholar] [CrossRef]
  31. Tamizhdurai, P.; Ramesh, A.; KriShnan, P.S.; Mangesh, V.L.; Umasankar, S.; Narayanan, S.; Ragupathi, C.; Shanthi, K. Hydrogenation of dicyclopentadiene into endo-tetrahydrodicyclopentadie over supported different metal catalysts. Microporous Mesoporous Mat. 2019, 290, 109678. [Google Scholar] [CrossRef]
  32. O’Driscoll, Á.; Leahy, J.J.; Curtin, T. The influence of metal selection on catalyst activity for the liquid phase hydrogenation of furfural to furfuryl alcohol. Catal. Today 2017, 279, 194–201. [Google Scholar] [CrossRef]
  33. Wang, L.; Chen, T.; Zhang, J.; Jiao, Y.; Wang, J.; Zhu, Q.; Li, X. High catalytic activity and stability quasi homogeneous alkali metal promoted Ni/SiO2 aerogel catalysts for catalytic cracking of n-decane. Fuel 2020, 268, 117384. [Google Scholar] [CrossRef]
  34. Zheng, Y.; Zhao, N.; Chen, J. Enhanced direct deoxygenation of anisole to benzene on SiO2-supported NiGa alloy and intermetallic compound. Appl. Catal. B-Environ. 2019, 250, 280–291. [Google Scholar] [CrossRef]
  35. Mahlaba, S.V.L.; Mahomed, A.S.; Friedrich, H.B. Regeneration of a 15% Ni/SiO2 phosphorus poisoned catalyst and subsequent effects of the support on recovery of the catalytic activity. Appl. Catal. A-Gen. 2018, 565, 163–169. [Google Scholar] [CrossRef]
  36. Li, B.; Zhang, B.; Guan, Q.; Chen, S.; Ning, P. Activity of Ni/CeO2 catalyst for gasification of phenol in supercritical water. Int. J. Hydrogen Energy 2018, 43, 19010–19018. [Google Scholar] [CrossRef]
  37. Zhao, C.; Wang, J.; Chen, X.; Liang, C. Nickel molybdenum bimetallic nitrides as efficient catalysts for the hydrodeoxygenation of methyl palmitate. Eur. J. Inorg. Chem. 2023, 26, e202300073. [Google Scholar] [CrossRef]
  38. Ren, S.; Zhang, P.; Shui, H.; Lei, Z.; Wang, Z.; Kang, S. Promotion of Ni/SBA-15 catalyst for hydrogenation of naphthalene by pretreatment with ammonia/water vapour. Catal. Commun. 2010, 12, 132–136. [Google Scholar] [CrossRef]
  39. Zhou, S.; Kang, L.; Xu, Z.; Zhu, M. Catalytic performance and deactivation of Ni/MCM-41 catalyst in the hydrogenation of pure acetylene to ethylene. RSC Adv. 2020, 10, 1937–1945. [Google Scholar] [CrossRef]
  40. Ghuge, S.P.; Saroha, A.K. Catalytic ozonation of dye industry effluent using mesoporous bimetallic Ru-Cu/SBA-15 catalyst. Process Saf. Environ. Protect. 2018, 118, 125–132. [Google Scholar] [CrossRef]
  41. Yin, Y.; Ren, Y.; Lu, J.; Zhang, W.; Shan, C.; Hua, M.; Lv, L.; Pan, B. The nature and catalytic reactivity of UiO-66 supported Fe3O4 nanoparticles provide new insights into Fe-Zr dual active centers in Fenton-like reactions. Appl. Catal. B-Environ. 2021, 286, 119943. [Google Scholar] [CrossRef]
  42. Liu, M.; Shi, Y.; Bi, Y.; Xing, E.; Wu, Y.; Huang, S.; Yang, M. Influence of porosity on product distribution over Co/H-ZSM-22 catalysts in the upgrading of palmitic acid. Energy Technol. 2018, 6, 406–415. [Google Scholar] [CrossRef]
  43. Liu, L.; Lou, H.; Chen, M. Selective hydrogenation of furfural to tetrahydrofurfuryl alcohol over Ni/CNTs and bimetallic Cu-Ni/CNTs catalysts. Int. J. Hydrogen Energy 2016, 41, 14721–14731. [Google Scholar] [CrossRef]
  44. Armenta, M.A.; Maytorena, V.M.; Flores-Sanchez, L.A.; Quintana, J.M.; Valdez, R.; Olivas, A. Dimethyl ether production via methanol dehydration using Fe3O4and CuO over γ-χ-Al2O3 nanocatalysts. Fuel 2020, 280, 118545. [Google Scholar] [CrossRef]
  45. Chen, H.; Lin, W.; Zhang, Z.; Yang, Z.; Jie, K.; Fu, J.; Yang, S.-Z.; Dai, S. Facile benzene reduction promoted by a synergistically coupled Cu-Co-Ce ternary mixed oxide. Chem. Sci. 2020, 11, 5766–5771. [Google Scholar] [CrossRef]
  46. Nie, X.; Zhang, Z.; Wang, H.; Guo, X.; Song, C. Effect of surface structure and Pd doping of Fe catalysts on the selective hydrodeoxygenation of phenol. Catal. Today 2021, 371, 189–203. [Google Scholar] [CrossRef]
  47. Zhao, B.; Liu, P.; Li, S.; Shi, H.; Jia, X.; Wang, Q.; Yang, F.; Song, Z.; Guo, C.; Hu, J.; et al. Bimetallic Ni-Co nanoparticles on SiO2 as robust catalyst for CO methanation: Effect of homogeneity of Ni-Co alloy. Appl. Catal. B-Environ. 2020, 278, 119307. [Google Scholar] [CrossRef]
  48. Audemar, M.; Ramdani, W.; Junhui, T.; Ifrim, A.; Ungureanu, A.; Jerome, F.; Royer, S.; Vigier, K.D.O. Selective hydrogenation of xylose to xylitol over Co/SiO2 catalysts. ChemCatChem 2020, 12, 1973–1978. [Google Scholar] [CrossRef]
  49. Huang, Z.; Barnett, K.J.; Chada, J.P.; Brentzel, Z.J.; Xu, Z.; Dumesic, J.A.; Huber, G.W. Hydrogenation of γ-butyrolactone to 1,4-butanediol over CuCo/TiO2 bimetallic catalysts. ACS Catal. 2017, 7, 8429–8440. [Google Scholar] [CrossRef]
  50. Huang, Z.; Chen, J.; Jia, Y.; Liu, H.; Xia, C.; Liu, H. Selective hydrogenolysis of xylitol to ethylene glycol and propylene glycol over copper catalysts. Appl. Catal. B-Environ. 2014, 147, 377–386. [Google Scholar] [CrossRef]
  51. Shao, Y.; Fan, M.; Sun, K.; Gao, G.; Li, C.; Li, D.; Jiang, Y.; Zhang, L.; Zhang, S.; Hu, X. The quantitative conversion of polyethylene terephthalate (PET) and Coca-Cola bottles to p-xylene over Co-based catalysts with tailored activities for deoxygenation and hydrogenation. Green Chem. 2023, 25, 10513–10529. [Google Scholar] [CrossRef]
  52. Yang, W.; Zhu, W.; Liu, H.; Niu, H.; Luo, J.; Liang, C. Regulating the coordination environment of Co@C catalysts for selective hydrogenation of adiponitrile to hexamethylenediamine. J. Catal. 2024, 430, 115312. [Google Scholar] [CrossRef]
  53. Bavykina, A.; Yarulina, I.; Al Abdulghani, A.J.; Gevers, L.; Hedhili, M.N.; Miao, X.; Galilea, A.R.; Pustovarenko, A.; Dikhtiarenko, A.; Cadiau, A.; et al. Turning a methanation Co catalyst into an In-Co methanol producer. ACS Catal. 2019, 9, 6910–6918. [Google Scholar] [CrossRef]
  54. Wezendonk, T.A.; Santos, V.P.; Nasalevich, M.A.; Warringa, Q.S.E.; Dugulan, A.I.; Chojecki, A.; Koeken, A.C.J.; Ruitenbeek, M.; Meima, G.; Islam, H.-U.; et al. Elucidating the nature of Fe species during pyrolysis of the Fe-BTC MOF into highly active and stable Fischer-Tropsch catalysts. ACS Catal. 2016, 6, 3236–3247. [Google Scholar] [CrossRef]
  55. Zhang, L.; Wang, Y.; Yang, Y.; Zhang, B.; Wang, S.; Lin, J.; Wan, S.; Wang, Y. Selective hydrogenolysis of aryl ether bond over Ru-Fe bimetallic catalyst. Catal. Today 2021, 365, 199–205. [Google Scholar] [CrossRef]
  56. Su, W.; Yang, J.; Zhang, M.; Zhao, Z.; Han, J.; Yang, Y.; Yang, J.-H.; Liu, Z. Highly dispersed and ultra-small Ru nanoparticles deposited on silica support as highly active and stable catalyst for biphenyl hydrogenation. Mol. Catal. 2021, 508, 111577. [Google Scholar] [CrossRef]
Catalysts 14 00727 g001
Figure 1. XRD patterns of the calcined 20%Ni/SiO2 catalysts with different SSAs.
Figure 1. XRD patterns of the calcined 20%Ni/SiO2 catalysts with different SSAs.
Catalysts 14 00727 g001
Catalysts 14 00727 g002
Figure 2. H2-TPR of 20%Ni/SiO2 catalysts with different SSAs.
Figure 2. H2-TPR of 20%Ni/SiO2 catalysts with different SSAs.
Catalysts 14 00727 g002
Catalysts 14 00727 g003
Figure 3. XRD patterns of 20%Ni/SiO2 catalysts with different SSAs after reduction.
Figure 3. XRD patterns of 20%Ni/SiO2 catalysts with different SSAs after reduction.
Catalysts 14 00727 g003
Catalysts 14 00727 g004
Figure 4. N2 adsorption–desorption isotherms (a) and pore size distribution (b) of 20%Ni/SiO2 catalysts with different SSAs.
Figure 4. N2 adsorption–desorption isotherms (a) and pore size distribution (b) of 20%Ni/SiO2 catalysts with different SSAs.
Catalysts 14 00727 g004
Catalysts 14 00727 g005
Figure 5. TEM images (a,c,e,g), along with the particle size distribution histograms (b,e,f,h) of 20%Ni/SiO2 catalysts with different SSAs. (a,b) 20% Ni/SiO2-100, (c,d) 20% Ni/SiO2-200, (e,f) 20% Ni/SiO2-300 and (g,h) 20% Ni/SiO2-400.
Figure 5. TEM images (a,c,e,g), along with the particle size distribution histograms (b,e,f,h) of 20%Ni/SiO2 catalysts with different SSAs. (a,b) 20% Ni/SiO2-100, (c,d) 20% Ni/SiO2-200, (e,f) 20% Ni/SiO2-300 and (g,h) 20% Ni/SiO2-400.
Catalysts 14 00727 g005
Catalysts 14 00727 g006
Figure 6. XRD patterns of the calcined 20%M/SiO2 (M = Cu, Co, Fe) catalysts.
Figure 6. XRD patterns of the calcined 20%M/SiO2 (M = Cu, Co, Fe) catalysts.
Catalysts 14 00727 g006
Catalysts 14 00727 g007
Figure 7. H2-TPR curves of 20%M/SiO2 (M = Cu, Co, Fe) catalysts.
Figure 7. H2-TPR curves of 20%M/SiO2 (M = Cu, Co, Fe) catalysts.
Catalysts 14 00727 g007
Catalysts 14 00727 g008
Figure 8. XRD patterns of the reduced 20%M/SiO2 (M = Cu, Co, Fe) catalysts.
Figure 8. XRD patterns of the reduced 20%M/SiO2 (M = Cu, Co, Fe) catalysts.
Catalysts 14 00727 g008
Catalysts 14 00727 g009
Figure 9. N2 adsorption–desorption isotherms (a) and pore size distributions (b) of 20%M/SiO2 (M = Cu, Co, Fe) catalysts.
Figure 9. N2 adsorption–desorption isotherms (a) and pore size distributions (b) of 20%M/SiO2 (M = Cu, Co, Fe) catalysts.
Catalysts 14 00727 g009
Catalysts 14 00727 g010
Figure 10. Catalytic performance of 20%Ni/SiO2 catalysts for the selective hydrogenation of BP (a) 20%Ni/SiO2-100, (b) 20%Ni/SiO2-200, (c) 20%Ni/SiO2-300 and (d) 20%Ni/SiO2-400.
Figure 10. Catalytic performance of 20%Ni/SiO2 catalysts for the selective hydrogenation of BP (a) 20%Ni/SiO2-100, (b) 20%Ni/SiO2-200, (c) 20%Ni/SiO2-300 and (d) 20%Ni/SiO2-400.
Catalysts 14 00727 g010
Catalysts 14 00727 g011
Figure 11. BP conversion, CHB selectivity, and CHB yield over 20%M/SiO2 catalysts: (a) 20%Co/SiO2, (b) 20%Ni/SiO2, (c) 20%Fe/SiO2, and (d) 20%Cu/SiO2.
Figure 11. BP conversion, CHB selectivity, and CHB yield over 20%M/SiO2 catalysts: (a) 20%Co/SiO2, (b) 20%Ni/SiO2, (c) 20%Fe/SiO2, and (d) 20%Cu/SiO2.
Catalysts 14 00727 g011
Catalysts 14 00727 g012
Figure 12. The recycling ability of 20% Ni/SiO2-300 catalyst in BP hydrogenation. Reaction conditions: Mcatalyst:MBP = 0.1, 40 mL of isopropanol, 2.0 MPa, T = 120 °C, t = 80 min, and stirring rate of 800 rpm.
Figure 12. The recycling ability of 20% Ni/SiO2-300 catalyst in BP hydrogenation. Reaction conditions: Mcatalyst:MBP = 0.1, 40 mL of isopropanol, 2.0 MPa, T = 120 °C, t = 80 min, and stirring rate of 800 rpm.
Catalysts 14 00727 g012
Table 1. Pore size distribution, SSA, and metal particle size of 20%Ni/SiO2 catalysts with different SSAs.
Table 1. Pore size distribution, SSA, and metal particle size of 20%Ni/SiO2 catalysts with different SSAs.
SampleSSA a
(m2·g−1)		Pore
Volume b
(cm3g−1)		Average Pore
Diameter b
(nm)		Metal Particle Size c
(nm)
20% Ni/SiO2-1001521.125.923.5
20% Ni/SiO2-2001641.126.323.4
20% Ni/SiO2-3002071.017.322.0
20% Ni/SiO2-4002291.019.319.8
a Calculated by the Brunauer–Emmett–Teller method. b Calculated by the Barrett–Joyner–Halenda method. c Calculated by Scherer’s formula.
Table 2. Statistical table for pore size distribution, SSA, and metal particle size of 20%M/SiO2 (M= Co, Cu, Fe) catalysts.
Table 2. Statistical table for pore size distribution, SSA, and metal particle size of 20%M/SiO2 (M= Co, Cu, Fe) catalysts.
SampleSSA a
(m2·g−1)		Pore
Volume b
(cm3g−1)		Average Pore
Diameter b
(nm)		Metal Particle Size c
(nm)
20%Co/SiO22161.220.823.1
20%Cu/SiO22041.221.719.2
20%Fe/SiO22121.120.324.3
a Calculated by the Brunauer–Emmett–Teller method. b Calculated by the Barrett–Joyner–Halenda method. c Calculated by Scherer’s formula.
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Fan, J.; Li, W.; Yang, J.; Yang, T.; Liu, Z.; Zhang, M. The Effects of Support Specific Surface Area and Active Metal on the Performance of Biphenyl Selective Hydrogenation to Cyclohexylbenzene. Catalysts 2024, 14, 727. https://doi.org/10.3390/catal14100727

AMA Style

Fan J, Li W, Yang J, Yang T, Liu Z, Zhang M. The Effects of Support Specific Surface Area and Active Metal on the Performance of Biphenyl Selective Hydrogenation to Cyclohexylbenzene. Catalysts. 2024; 14(10):727. https://doi.org/10.3390/catal14100727

Chicago/Turabian Style

Fan, Jie, Wei Li, Jingyi Yang, Tao Yang, Zhongyi Liu, and Meng Zhang. 2024. "The Effects of Support Specific Surface Area and Active Metal on the Performance of Biphenyl Selective Hydrogenation to Cyclohexylbenzene" Catalysts 14, no. 10: 727. https://doi.org/10.3390/catal14100727

APA Style

Fan, J., Li, W., Yang, J., Yang, T., Liu, Z., & Zhang, M. (2024). The Effects of Support Specific Surface Area and Active Metal on the Performance of Biphenyl Selective Hydrogenation to Cyclohexylbenzene. Catalysts, 14(10), 727. https://doi.org/10.3390/catal14100727

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop