RESEARCH ARTICLE

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

  • Yi-Fan Xue ,
  • Jie Feng ,
  • Yun-Cai Song ,
  • Wen-Ying Li
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  • State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China
fengjie@tyut.edu.cn

Received date: 16 Feb 2023

Accepted date: 27 Apr 2023

Published date: 15 Dec 2023

Copyright

2023 Higher Education Press

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.

Cite this article

Yi-Fan Xue , Jie Feng , Yun-Cai Song , Wen-Ying Li . Effect of noble metal nanoparticle size on C–N bond cleavage performance in hydrodenitrogenation: a study of active sites[J]. Frontiers of Chemical Science and Engineering, 2023 , 17(12) : 1986 -2000 . DOI: 10.1007/s11705-023-2337-5

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.
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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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

DOI

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