Effect of noble metal nanoparticle size on C–N bond cleavage performance in hydrodenitrogenation: a study of active sites

Abstract

Breakage of the C–N bond is a structure sensitive process, and the catalyst size significantly affects its activity. On the active metal nanoparticle scale, the role of catalyst size in C–N bond cleavage has not been clearly elucidated. So, Ru catalysts with variable nanoparticle sizes were obtained by modulating the reduction temperature, and the catalytic activity was evaluated using 1,2,3,4-tetrahydroquinoline and o-propylaniline with different C–N bond hybridization patterns as reactants. Results showed a 13 times higher reaction rate for sp³-hybridized C–N bond cleavage than sp²-hybridized C–N bond cleavage, while the reaction rate tended to increase first and then decrease as the catalyst nanoparticle size increased. Different concentrations of terrace, step, and corner sites were found in different sizes of Ru nanoparticles. The relationship between catalytic site variation and C–N bond cleavage activity was further investigated by calculating the turnover frequency values for each site. This analysis indicates that the variation of different sites on the catalyst is the intrinsic factor of the size dependence of C–N bond cleavage activity, and the step atoms are the active sites for the C–N bond cleavage. When Ru nanoparticles are smaller than 1.9 nm, they have a strong adsorption effect on the reactants, which will affect the catalytic performance of the Ru catalyst. Furthermore, these findings were also confirmed on other metallic Pd/Pt catalysts. The role of step sites in C–N bond cleavage was proposed using the density function theory calculations. The reactants have stronger adsorption energies on the step atoms, and step atoms have d-band center nearer to the Fermi level. In this case, the interaction with the reactant is stronger, which is beneficial for activating the C–N bond of the reactant.

Key words： sp³/sp²-hybridized C–N bond; noble metal nanoparticle; catalytic active site; turnover frequency; DFT

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was supported by the Key Project of National Natural Science Foundation of China (Grant No. 22038008), the Science and Technology Innovation Project of National Energy Group China Shenhua Coal to Oil Chemical Co. (Grant No. MZYHG-2021-01).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at http://doi.org/10.1007/s11705-023-2337-5 and is accessible for authorized users.

References

1 Ferdous D, Dalai A K, Adjaye J. Hydrodenitrogenation and hydrodesulfurization of heavy gas oil using NiMo/Al₂O₃ catalyst containing boron: experimental and kinetic studies. Industrial & Engineering Chemistry Research, 2006, 45(2): 544–552

2 Piskorz W, Adamski G, Kotarba A, Sojka Z, Sayag C, Djéga-Mariadassou G. Hydrodenitrogenation of indole over Mo₂C catalyst: insights into mechanistic events through DFT modeling. Catalysis Today, 2007, 119(1–4): 39–43

3 Ozkan U S, Ni S, Zhang L, Moctezuma E. Simultaneous hydrodesulfurization and hydrodenitrogenation of model compounds over nickel-molybdenum/γ-Al₂O₃ catalysts. Energy & Fuels, 1994, 8(1): 249–257

4 Saleh T A, Al-Hammadi S A. A novel catalyst of nickel-loaded graphene decorated on molybdenum-alumina for the HDS of liquid fuels. Chemical Engineering Journal, 2021, 406: 125167

5 Wang H M, Liang C H, Prins R. Hydrodenitrogenation of 2-methylpyridine and its intermediates 2-methylpiperidine and tetrahydro-methylpyridine over sulfided NiMo/γ-Al₂O₃. Journal of Catalysis, 2007, 251(2): 295–306

6 Wang W, Li X, Sun Z C, Wang A J, Liu Y, Chen Y Y, Duan X P. Influences of calcination and reduction methods on the preparation of Ni₂P/SiO₂ and its hydrodenitrogenation performance. Applied Catalysis A, General, 2016, 509: 45–51

7 Santen R. A v, Neurock M, Shetty S G. Reactivity theory of transition-metal surfaces: a Brønsted-Evans-Polanyi linear activation energy-free-energy analysis. Chemical Reviews, 2010, 110(4): 2005–2048

8 Eijsbouts S, Sudhakar C. Beer d V H J, Prins R. Hydrodenitrogenation of decahydroquinoline, cyclohexylamine and o-propylaniline over carbon-supported transition metal sulfide catalysts. Journal of Catalysis, 1991, 127(2): 605–618

9 Guo Y, He H, Liu X, Chen Z, Rioux R M, Janik M J, Savage P E. Ring-opening and hydrodenitrogenation of indole under hydrothermal conditions over Ni, Pt, Ru, and Ni-Ru bimetallic catalysts. Chemical Engineering Journal, 2021, 406: 126853

10 Ledesma B C, Anunziata O A, Beltramone A R. HDN of indole over Ir-modified Ti-SBA-15. Applied Catalysis B: Environmental, 2016, 192(5): 220–233

11 Guttieri M J, Maier W F. Selective cleavage of carbon-nitrogen bonds with platinum. Journal of Organic Chemistry, 1984, 49(16): 2875–2880

12 Oyama S T. Novel catalysts for advanced hydroprocessing: transition metal phosphides. Journal of Catalysis, 2003, 216(1–2): 343–352

13 Li Z, Ji S F, Liu Y W, Cao X, Tian S B, Chen Y J, Niu Z Q, Li Y D. Well-defined materials for heterogeneous catalysis: from nanoparticles to isolated single-atom sites. Chemical Reviews, 2020, 120(2): 623–682

14 Liu L C, Corma A. Metal catalysts for heterogeneous catalysis: from single atoms to nanoclusters and nanoparticles. Chemical Reviews, 2018, 118(10): 4981–5079

15 Chen W Y, Ji J, Feng X, Duan X Z, Qian G, Li P, Zhou X G, Chen D, Yuan W K. Mechanistic insight into size-dependent activity and durability in Pt/CNT catalyzed hydrolytic dehydrogenation of ammonia borane. Journal of the American Chemical Society, 2014, 136(48): 16736–16739

16 Yang F F, Liu D, Zhao Y T, Wang H, Han J Y, Ge Q F, Zhu X L. Size dependence of vapor phase hydrodeoxygenation of m-cresol on Ni/SiO₂ catalysts. ACS Catalysis, 2018, 8(3): 1672–1682

17 Ma J Y, Tan X J, Zhang Q Q, Wang Y, Zhang J L, Wang L Z. Exploring the size effect of Pt nanoparticles on the photocatalytic nonoxidative coupling of methane. ACS Catalysis, 2021, 11(6): 3352–3360

18 Tsung C K, Kuhn J N, Huang W Y, Aliaga C, Hung L I, Somorjai G A, Yang P D. Sub-10 nm platinum nanocrystals with size and shape control: catalytic study for ethylene and pyrrole hydrogenation. Journal of the American Chemical Society, 2009, 131(16): 5816–5822

19 Liu J, Li W Y, Feng J, Gao X. Molecular insights into the hydrodenitrogenation mechanism of pyridine over Pt/γ-Al₂O₃ catalysts. Molecular Catalysis, 2020, 495: 111148

20 Liuzzi D, Pérez-Alonso F J, García-García F J, Calle-Vallejo F, Fierro J L G, Rojas S. Identifying the time-dependent predominance regimes of step and terrace sites for the Fischer-Tropsch synthesis on ruthenium based catalysts. Catalysis Science & Technology, 2016, 6(17): 6495–6503

21 Chiu C C, Genest A, Borgna A, Rösch N. C–O cleavage of aromatic oxygenates over ruthenium catalysts. A computational study of reactions at step sites. Physical Chemistry Chemical Physics, 2015, 17(23): 15324–15330

22 Kuhn J N, Huang W, Tsung C K, Zhang Y, Somorjai G A. Structure sensitivity of carbon-nitrogen ring opening: impact of platinum particle size from below 1 to 5 nm upon pyrrole hydrogenation product selectivity over monodisperse platinum nanoparticles loaded onto mesoporous silica. Journal of the American Chemical Society, 2008, 130(43): 14026–14027

23 Bachrach M, Marks T J, Notestein J M. C–N bond hydrogenolysis of aniline and cyclohexylamine over TaO_x-Al₂O₃. New Journal of Chemistry, 2016, 40(7): 6001–6004

24 Sureshkumar K, Shanthi K, Sasirekha N R, Jegan J, Sardhar Basha S J. A study on catalytic activity of modified Ni-Re/Al-SBA-15 catalyst for hydrodenitrogenation of o-toluidine. International Journal of Hydrogen Energy, 2020, 45(7): 4328–4340

25 Sardhar Basha S J, Sasirekha N R, Maheswari R, Shanthi K. Mesoporous H-AlMCM-41 supported NiO-MoO₃ catalysts for hydrodenitrogenation of o-toluidine. Applied Catalysis A, General, 2006, 308: 91–98

26 Carballo J M G, Yang J, Holmen A, García-Rodríguez S, Rojas S, Ojeda M, Fierro J L G. Catalytic effects of ruthenium particle size on the Fischer-Tropsch synthesis. Journal of Catalysis, 2011, 284(1): 102–108

27 Murata K, Onoda J, Yamamoto Y, Oda A, Ohyama J, Satsuma A. Enhancement of toluene hydrogenation activity of supported Pt nanoparticles with increasing the crystallinity of Pt. Applied Catalysis A, General, 2022, 629: 118425

28 Iwamoto M, Akiyama M, Aihara K, Deguchi T. Ammonia synthesis on wool-like Au, Pt, Pd, Ag, or Cu electrode catalysts in nonthermal atmospheric-pressure plasma of N₂ and H₂. ACS Catalysis, 2017, 7(10): 6924–6929

29 Zhao Z S, Wang M, Cui L, He J L, Yu D L, Tian Y J. Semiconducting superhard ruthenium monocarbide. Journal of Physical Chemistry C, 2010, 114(21): 9961–9964

30 Zhang C Z, Kuang X Y, Jin Y Y, Lu C, Zhou D W, Li P F, Bao G, Hermann A. Prediction of stable ruthenium silicides from first-principles calculations: stoichiometries, crystal structures, and physical properties. ACS Applied Materials & Interfaces, 2015, 7(48): 26776–26782

31 Prins R. Catalytic hydrodenitrogenation. Advances in Catalysis, 2001, 46: 399–464

32 Wilson O M, Knecht M R, Garcia-Martinez J C, Crooks R M. Effect of Pd nanoparticle size on the catalytic hydrogenation of allyl alcohol. Journal of the American Chemical Society, 2006, 128(14): 4510–4511

33 Hardeveld R V, Hartog F. The statistics of surface atoms and surface sites on metal crystals. Surface Science, 1969, 15(2): 189–230

34 Kolpin A, Jones G, Jones S, Zheng W, Cookson J, York A P E, Collier P J, Tsang S C E. Quantitative differences in sulfur poisoning phenomena over ruthenium and palladium: an attempt to deconvolute geometric and electronic poisoning effects using model catalysts. ACS Catalysis, 2016, 7(1): 592–605

35 Abdel-Mageed A M, Widmann D, Olesen S E, Chorkendorff I, Biskupek J, Behm R J. Selective CO methanation on Ru/TiO₂ catalysts: role and influence of metal-support interactions. ACS Catalysis, 2015, 5(11): 6753–6763

36 Peng X B, Chen X C, Zhou Y L, Sun F X, Zhang T H, Zheng L R, Jiang L L, Wang X Y. Size-dependent activity of supported Ru catalysts for ammonia synthesis at mild conditions. Journal of Catalysis, 2022, 408: 98–108

37 Zheng J W, Liao F L, Wu S, Jones G, Chen T Y, Fellowes J, Sudmeier T, McPherson I J, Wilkinson I, Tsang S C E. Efficient non-dissociative activation of dinitrogen to ammonia over lithium-promoted ruthenium nanoparticles at low pressure. Angewandte Chemie International Edition, 2019, 58(48): 17335–17341

38 Chin S Y, Williams C T, Amiridis M D. FTIR studies of CO adsorption on Al₂O₃- and SiO₂-supported Ru catalysts. Journal of Physical Chemistry B, 2006, 110(2): 871–882

39 Kim Y K, Gregg A, Morgan J, John T, Yates J. Role of atomic step defect sites on the catalytic oxidation of carbon monoxide: comparison between Ru(001) and Ru(109) single-crystal surfaces. Journal of Physical Chemistry C, 2007, 111(8): 3366–3368

40 Li D L, Lu M M, Aragaki K, Koike M, Nakagawa Y, Tomishige K. Characterization and catalytic performance of hydrotalcite-derived Ni-Cu alloy nanoparticles catalysts for steam reforming of 1-methylnaphthalene. Applied Catalysis B: Environmental, 2016, 192: 171–181

41 Oyama S T, Lee Y K. Mechanism of hydrodenitrogenation on phosphides and sulfides. Journal of Physical Chemistry B, 2005, 109(6): 2109–2119

42 Nørskov J K. Electronic factors in catalysis. Progress in Surface Science, 1991, 38(2): 103–144

43 Liu J, Li W Y, Feng J, Gao X, Luo Z Y. Promotional effect of TiO₂ on quinoline hydrodenitrogenation activity over Pt/γ-Al₂O₃ catalysts. Chemical Engineering Science, 2019, 207: 1085–1095

44 Liu J, Li W Y, Feng J, Gao X. Effects of Fe species on promoting the dibenzothiophene hydrodesulfurization over the Pt/γ-Al₂O₃ catalysts. Catalysis Today, 2020, 371: 247–257

45 Ledoux M J, Djellouli B. Hydrodenitrogenation activity and selectivity of well-dispersed transition metal sulfides of the second row on activated carbon. Journal of Catalysis, 1989, 115(2): 580–590

46 Zhang Z L, Zhu Y H, Asakura H, Zhang B, Zhang J G, Zhou M X, Han Y, Tanaka T, Wang A Q, Zhang T, Yan N. Thermally stable single atom Pt/m-Al₂O₃ for selective hydrogenation and CO oxidation. Nature Communications, 2017, 8(1): 16100

47 Hofmann T, Yu T H, Folse M, Weinhardt L, Bär M, Zhang Y, Merinov B V, Myers D J, Goddard W A III, Heske C. Using photoelectron spectroscopy and quantum mechanics to determine d-band energies of metals for catalytic applications. Journal of Physical Chemistry C, 2012, 116(45): 24016–24026

48 Kim M, Park G H, Seo S, Bui V Q, Cho Y, Hong Y, Kawazoe Y, Lee H. Uncovering the role of countercations in ligand exchange of WSe₂: tuning the d-band center toward improved hydrogen desorption. ACS Applied Materials & Interfaces, 2021, 13(9): 11403–11413

49 Henckel D A, Lenz O, Cossairt B M. Effect of ligand coverage on hydrogen evolution catalyzed by colloidal WSe₂. ACS Catalysis, 2017, 7(4): 28152820