Remote hydrogen-spillover effect on catalytic transnitrilation for biomass-based nitrile synthesis

doi:10.1016/S1872-2067(25)64782-6

Abstract

Abstract:

Acid-nitrile exchange reaction (transnitrilation) is a state-of-the-art strategy for nitrile synthesis with a promising industrial application. Herein, a dedicated catalytic system for transnitrilation was designed based on remote H-spillover effect by physically mixing Pt nanoparticles-encapsulated in hollow ZSM-5 (Pt@ZSM-5) and Ni-doped Nb₂O₅ (Ni/Nb₂O₅) under 10%-H₂/N₂. The Pt@ZSM-5 acts as a primary active-center for H₂-dissociation over Pt to form H-spillover; while, Ni/Nb₂O₅ serves as an acceptor-site of H-spillover. Upon uptake of the H-spillover, the doped-reversible Ni²⁺/Ni⁺ couples in the Ni/Nb₂O₅ significantly facilitate migrations of proton (Brönsted-acid site) and surface vacancy (Lewis-acid site) throughout its surface, thus enhancing and enriching its surface-acidic sites for the catalytic transnitrilation. Kinetic analysis demonstrates nitrile-activation over Lewis-acid site of Ni/Nb₂O₅ as rate-determining step of the transnitrilation. This research provides a molecular-scale and fundamental understanding of remote H-spillover effect on a solid acid for an improved catalytic performance by in-situ regulation on its surface-acid type and strength.

Key words: Acidity, Biomass, Hydrogen spillover, Surface vacancy, Transnitrilation

Guipeng Zhang, Yan Bin, Yanxin Wang, Jinzhu Chen. Remote hydrogen-spillover effect on catalytic transnitrilation for biomass-based nitrile synthesis[J]. Chinese Journal of Catalysis, 2025, 77: 153-170.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64782-6

https://www.cjcatal.com/EN/Y2025/V77/I10/153

Figures/Tables 15

Fig. 1. Ni/Nb2O5: TEM images (a,b), TEM-EDS (c,d), and elemental-mapping (e-g). Pt@ZSM-5: TEM images (h,i), TEM-EDS (j,k), and elemental-mapping (l-o).

Fig. 2. Structural characterization. (a) N2 adsorption-desorption isotherms with pore size distribution curves. (b) Ni 2p XPS of Ni/Nb2O5. (c) Nb 3d XPS of Ni/Nb2O5 and Nb2O5. (d) O 1s XPS of Ni/Nb2O5 and Nb2O5. (e) XRD patterns of Pt@ZSM-5. (f) Pt 4f XPS of Pt@ZSM-5.

Table 1 Structural parameters of the Nb2O5, Ni/Nb2O5 and Pt@ZSM-5.

Sample	S_BET^a (m² g^-1)	S_micro^b (m² g^-1)	S_ext^c (m² g^-1)	Average pore size^d (nm)	V_total^e (cm³ g^-1)	V_micro^f/V_ext^g (cm³ g^-1)
Nb₂O₅	98	76	22	4.0	0.10	0.04/0.06
7.6%-Ni/Nb₂O₅	202	0	202	17	0.17	0/0.17
2.7%-Pt@ZSM-5	393	388	5	4.8	0.47	0.15/0.32

Fig. 3. 1a/2a-transnitrilation over various catalysts. Reaction conditions: catalyst (Nb2O5, 7.6%-Ni/Nb2O5 and 2.7%-Pt@ZSM-5, 10 mg respectively), 2a (3.0 mL), 1a (0.10 mmol), N2 (1.5 MPa), 190 °C, 6.0 h. aUnder 10%-H2/N2 (1.5 MPa) instead of N2 (1.5 MPa).

Fig. 4. 1a/2a-transnitrilation over Ni/Nb2O5-Pt@ZSM-5: product-distribution against reaction-time under N2 for (a) and 10%-H2/N2 for (b), product-distribution against reaction-temperature under N2 for (c) and 10%-H2/N2 for (d), the effect of Ni/Nb2O5:Pt@ZSM-5 mass ratio (e) and catalyst loading level (f) on product-distribution. Reaction conditions: 7.6%-Ni/Nb2O5 10 mg, 2.7%-Pt@ZSM-5 10 mg, 2a 3.0 mL, 1a 0.10 mmol, 190 °C, N2 or 10%-H2/N2 1.5 MPa, 6.0 h. Specified reaction time for panels (a) and (b), specified reaction temperature for panels (c) and (d), specified Ni/Nb2O5:Pt@ZSM-5 mass ratio for panel (e), specified catalyst loading-level for panel (f).

Fig. 5. (a) H2-TPR profiles of investigated samples. FT-IR spectra of adsorbed probe-molecules on Ni/Nb2O5-Pt@ZSM-5 surface respectively under N2 and 10%-H2/N2: pyridine (b), phenylacetonitrile (c), and acetic acid (d).

Scheme 1. (a) Remote H-spillover effect on surface acidity of Ni/Nb2O5. (b) Proposed mechanism of Ni/Nb2O5-Pt@ZSM-5 promoted transnitrilation.

Scheme 2. (a) Remote H-spillover induced migration of active species (proton/electron pair, vacancy and -OH group) on the surface of reducible Ni/Nb2O5. (b) Remote H-spillover effect on the surface acidity of Nb2O5.

Fig. 6. FT-IR spectra of adsorbed probe molecules on Nb2O5-Pt@ZSM-5 surface respectively under N2 and 10%-H2/N2: pyridine (a), phenylacetonitrile (b), and acetic acid (c). Raman spectra of samples pretreated with N2 and H2: Ni/Nb2O5 (d) and Nb2O5 (e). (f) O2-TPD profiles of Ni/Nb2O5 and Nb2O5. Photographs of H-spillover for investigated WO3 (g), WO3-Ni/Nb2O5 (h), WO3-Pt@ZSM-5 (i), WO3-Ni/Nb2O5-Pt@ZSM-5 (j), and WO3-Nb2O5-Pt@ZSM-5 (k) samples.

Scheme 3. Control experiments. Reaction conditions: 7.6%-Ni/Nb2O5 10 mg, 2.7%-Pt@ZSM-5 10 mg, 190 °C, 6.0 h, 10%-H2/N2 1.5 MPa. 1a 0.10 mmol and 2a 3.0 mL for panel (a); 1a 0.10 mmol, 8a 0.50 mmol and toluene 3.0 mL for panel (b); 6a 0.10 mmol and 2a 3.0 mL for panel (c); 7a 0.10 mmol and 2a 3.0 mL for panel (d).

Scheme 4. Kinetic model of 1a/2a-transnitrilation.

Table 2 Kinetic parameters of 1a/2a-transnitrilation network as shown in Scheme 4a.

Run	T (°C)	k₁′ × 10 (h^-1)	E_a,1′ (kJ mol^-1)	lnA₁′ (h^-1)	k₃′ (h^-1)	E_a_,3′ (kJ mol^-1)	lnA₃′ (h^-1)
1^b	170	(2.25 ± 0.01)	53.8 ± 2.4	13.12 ± 0.66	1.04 ± 0.01	36.6 ± 2.1	9.95 ± 0.55
2^b	180	(3.21 ± 0.01)	53.8 ± 2.4	13.12 ± 0.66	1.23 ± 0.01	36.6 ± 2.1	9.95 ± 0.55
3^b	190	(4.12 ± 0.01)	53.8 ± 2.4	13.12 ± 0.66	1.58 ± 0.01	36.6 ± 2.1	9.95 ± 0.55
4^b	200	(5.79 ± 0.02)	53.8 ± 2.4	13.12 ± 0.66	1.92 ± 0.02	36.6 ± 2.1	9.95 ± 0.55
5^c	170	(5.31 ± 0.03)	34.6 ± 1.8	8.78 ± 0.49	1.13 ± 0.02	35.3 ± 2.1	9.68 ± 0.56
6^c	180	(6.83 ± 0.01)	34.6 ± 1.8	8.78 ± 0.49	1.34 ± 0.01	35.3 ± 2.1	9.68 ± 0.56
7^c	190	(8.15 ± 0.01)	34.6 ± 1.8	8.78 ± 0.49	1.64 ± 0.01	35.3 ± 2.1	9.68 ± 0.56
8^c	200	(9.70 ± 0.02)	34.6 ± 1.8	8.78 ± 0.49	2.08 ± 0.03	35.3 ± 2.1	9.68 ± 0.56

Fig. 7. Comparison of kinetic parameters in 1a/2a-transnitrilation at 190 °C under various conditions. (a) k′ and Ea′; (b) k1′ and k3′.

Fig. 8. Substrate scope of the transnitrilation reaction. Reaction conditions: 7.6%-Ni/Nb2O5 10 mg, 2.7%-Pt@ZSM-5 10 mg, 2a 3.0 mL, 1 0.10 mmol, 190 °C, 6.0 h, 10%-H2/N2 1.5 MPa. 1 Conversions (% in brackets) and 3 yields (%) were obtained by HPLC analysis.a 210 °C was used. b Determined by GC analysis.

Fig. 9. 1a/2a-transnitrilation over Ni/Nb2O5-Pt@ZSM-5 under H2/N2: hot-filtration (a) and catalyst reusability (b). Reaction conditions: 7.6%-Ni/Nb2O5 10 mg, 2.7%-Pt@ZSM-5 10 mg, 2a 3.0 mL, 1a 0.10 mmol, 190 °C, 6 h, 10%-H2/N2 1.5 MPa.

References

[1]	H. Dai, H. Guan, ACS Catal., 2018, 8, 9125-9130.
[2]	S. Elangovan, C. Topf, S. Fischer, H. Jiao, A. Spannenberg, W. Baumann, R. Ludwig, K. Junge, M. Beller, J. Am. Chem. Soc., 2016, 138, 8809-8814.
[3]	B. Paul, M. Maji, S. Kundu, ACS Catal., 2019, 9, 10469-10476.
[4]	X.-L. Tang, P.-F. Wen, W. Zheng, X.-Y. Zhu, Y. Zhang, H.-J. Diao, R.-C. Zheng, Y.-G. Zheng, ACS Catal., 2023, 13, 10282-10294.
[5]	Z. Guan, S. Zhu, S. Wang, H. Wang, S. Wang, X. Zhong, F. Bu, H. Cong, A. Lei, Angew. Chem. Int. Ed., 2021, 60, 1573-1577.
[6]	V. K. Chenniappan, S. Silwal, R. J. Rahaim, ACS Catal., 2018, 8, 4539-4544.
[7]	Q. You, D. B. Collum, J. Am. Chem. Soc., 2023, 145, 23568-23584.
[8]	D. Sun, E. Kitamura, Y. Yamada, S. Sato, Green Chem., 2016, 18, 3389-3396.
[9]	H. Okabe, A. Naraoka, T. Isogawa, S. Oishi, H. Naka, Org. Lett., 2019, 21, 4767-4770.
[10]	L. R. Mills, J. M. Graham, P. Patel, S. A. L. Rousseaux, J. Am. Chem. Soc., 2019, 141, 19257-19262.
[11]	M. S. Ahmad, B. Zeng, R. Qasim, D. Zheng, Q. Zhang, Y. Jin, Q. Wang, K. Meguellati, ACS Catal., 2024, 14, 2350-2357.
[12]	Z. Li, G.-A. Zhang, Y. Song, M. Li, Z. Li, W. Ding, J. Wu, Org. Lett., 2023, 25, 3023-3028.
[13]	X.-L. Lai, M. Chen, Y. Wang, J. Song, H.-C. Xu, J. Am. Chem. Soc., 2022, 144, 20201-20206.
[14]	S. Chen, D. Ding, L. Yin, X. Wang, J. A. Krause, W. Liu, J. Am. Chem. Soc., 2024, 146, 31982-31991.
[15]	A. W. Schuppe, G. M. Borrajo-Calleja, S. L. Buchwald, J. Am. Chem. Soc., 2019, 141, 18668-18672.
[16]	D. Cantillo, C. O. Kappe, J. Org. Chem., 2013, 78, 10567-10571.
[17]	D. A. Klein, J. Org. Chem., 1971, 36, 3050-3051.
[18]	K. Mlinarić-Majerski, R. Margeta, J. Veljković, Synlett, 2005, 2089-2091.
[19]	D. Cartigny, A. Dos Santos, L. El Kaïm, L. Grimaud, R. Jacquot, P. Marion, Synthesis, 2014, 46, 1802-1806.
[20]	G. Zhang, C. Zhang, Y. Tian, F. Chen, Org. Lett., 2023, 25, 917-922.
[21]	M. S. Li, J. Zhang, Chem. Eur. J., 2023, 29, e202300217.
[22]	L. Vanoye, A. Hammoud, H. Gérard, A. Barnes, R. Philippe, P. Fongarland, C. de Bellefon, A. Favre-Réguillon, ACS Catal., 2019, 9, 9705-9714.
[23]	R. I. Khusnutdinov, N. A. Shchadneva, A. R. Bayguzina, Y. Y. Mayakova, Russ. J. Org. Chem., 2016, 52, 1282-1286.
[24]	C. Marquez, M. Corbet, S. Smolders, P. Marion, D. De Vos, Chem. Commun., 2019, 55, 12984-12987.
[25]	W. Karim, C. Spreafico, A. Kleibert, J. Gobrecht, J. VandeVondele, Y. Ekinci, J. A. van Bokhoven, Nature, 2017, 541, 68-71.
[26]	X.-J. Bai, C. Yang, Z. Tang, Nat. Commun., 2024, 15, 6263.
[27]	H. Kim, J. H. Park, J.-M. Ha, D. H. Kim, ACS Catal., 2023, 13, 11857-11870.
[28]	S. Boonpai, K. Suriye, B. Jongsomjit, J. Panpranot, P. Praserthdam, Catal. Today, 2020, 358, 370-386.
[29]	H. D. Setiabudi, A. A. Jalil, S. Triwahyono, J. Catal., 2012, 294, 128-135.
[30]	X. Li, Z. Tong, S. Zhu, Q. Deng, S. Chen, J. Wang, Z. Zeng, Y. Zhang, J.-J. Zou, S. Deng, J. Catal., 2022, 405, 363-372.
[31]	Q. Deng, R. Zhou, Y.-C. Zhang, X. Li, J. Li, S. Tu, G. Sheng, J. Wang, Z. Zeng, T. Yoskamtorn, S. C. Edman Tsang, Angew. Chem. Int. Ed., 2023, 62, e202211461.
[32]	J. He, S. P. Burt, M. Ball, D. Zhao, I. Hermans, J. A. Dumesic, G. W. Huber, ACS Catal., 2018, 8, 1427-1439.
[33]	S. Triwahyono, A. A. Jalil, R. R. Mukti, M. Musthofa, N. A. M. Razali, M. A. A. Aziz, Appl. Catal. A, 2011, 407, 91-99.
[34]	T. Shishido, H. Hattori, J. Catal., 1996, 161, 194-197.
[35]	R. N. Olcese, M. Bettahar, D. Petitjean, B. Malaman, F. Giovanella, A. Dufour, Appl. Catal. B, 2012, 115, 63-73.
[36]	S. M. A. H. Siddiki, M. N. Rashed, M. A. Ali, T. Toyao, P. Hirunsit, M. Ehara, K.-I. Shimizu, ChemCatChem, 2019, 11, 383-396.
[37]	K. Nakajima, Y. Baba, R. Noma, M. Kitano, J. N. Kondo, S. Hayashi, M. Hara, J. Am. Chem. Soc., 2011, 133, 4224-4227.
[38]	P. Hirunsit, T. Toyao, S. M. A. H. Siddiki, K. Shimizu, M. Ehara, ChemPhysChem, 2018, 19, 2848-2857.
[39]	K. V. R. Chary, K. S. Lakshmi, P. V. R. Rao, K. S. R. Rao, M. Papadaki, J. Mol. Catal. A, 2004, 223, 353-361.
[40]	W. Jiang, J.-P. Cao, C. Zhu, T. Xie, X.-Y. Zhao, M. Zhao, Y.-P. Zhao, H.-C. Bai, Fuel, 2021, 295, 120635.
[41]	Z. Zhang, H. Xu, H. Li, Fuel, 2022, 324, 124400.
[42]	C. Dong, R. Mu, R. Li, J. Wang, T. Song, Z. Qu, Q. Fu, X. Bao, J. Am. Chem. Soc., 2023, 145, 17056-17065.
[43]	K. Shun, K. Mori, S. Masuda, N. Hashimoto, Y. Hinuma, H. Kobayashi, H. Yamashita, Chem. Sci., 2022, 13, 8137-8147.
[44]	A. S. Poyraz, C.-H. Kuo, S. Biswas, C. K. King’ondu, S. L. Suib, Nat. Commun., 2013, 4, 2952.
[45]	S. Yang, J. Chen, ACS Catal., 2023, 13, 113-131.
[46]	Z. Yu, W. Kong, Y. Guo, W. Liang, J. Liang, M. Chen, D. Zhao, H. Ma, X. Liu, S. Inalegwu Okopi, L. Che, Q. Zhang, Z. Sun, F. Xu, Fuel, 2024, 373, 132297.
[47]	L. Wolski, K. Sobańska, A. Walkowiak, K. Akhmetova, J. Gryboś, M. Frankowski, M. Ziolek, P. Pietrzyk, J. Hazard. Mater., 2021, 415, 125665.
[48]	L. Kong, C. Zhang, J. Wang, W. Qiao, L. Ling, D. Long, Sci. Rep., 2016, 6, 21177.
[49]	H. Zhu, R. Wang, J. Mater. Chem. A, 2022, 10, 12269-12277.
[50]	Y. Chen, G. Lv, X. Zou, S. Su, J. Wang, C. Zhou, J. Shen, Y. Shen, Z. Liu, J. Colloid Interface Sci., 2024, 664, 626-639.
[51]	L. Deng, Z. Wang, X. Yu, C. Qiao, S. Zhou, Q. Deng, Y. Zhao, Y. Tian, ACS Catal., 2024, 14, 16748-16758.
[52]	G. Xu, X. Zhu, Appl. Catal. B, 2021, 293, 120241.
[53]	S. Hu, Z.-A. Li, Chem. Eng. J., 2023, 471, 144828.
[54]	R. Crisafulli, V. V. S. de Barros, F. E. Rodrigues de Oliveira, T. de Araújo Rocha, S. Zignani, L. Spadaro, A. Palella, J. A. Dias, J. J. Linares, Appl. Catal. B, 2018, 236, 36-44.
[55]	L. Rakočević, J. Golubović, D. Vasiljević Radović, V. Rajić, S. Štrbac, Int. J. Hydrogen Energy, 2024, 51, 1240-1254.
[56]	S. G. Bratsch, J. Phys. Chem. Ref. Data, 1989, 18, 1-21.
[57]	R. Prins, Chem. Rev., 2012, 112, 2714-2738.
[58]	M. Xiong, Z. Gao, Y. Qin, ACS Catal., 2021, 11, 3159-3172.
[59]	J. Im, H. Shin, H. Jang, H. Kim, M. Choi, Nat. Commun., 2014, 5, 3370.
[60]	M. M. Hossain, M. A. Al-Saleh, M. A. Shalabi, T. Kimura, T. Inui, Appl. Catal. A, 2004, 274, 43-48.
[61]	J. He, Q.-J. Li, Y.-N. Fan, J. Solid State Chem., 2013, 202, 121-127.
[62]	H. Zou, Y. Jin, L. Chen, J. Chen, ACS Catal., 2025, 15, 2017-2032.
[63]	H. Kim, S. Yang, Y. H. Lim, J. Lee, J.-M. Ha, D. H. Kim, J. Catal., 2022, 410, 93-102.
[64]	M. L. Kuznetsov, Russ. Chem. Rev., 2002, 71, 265-282.
[65]	N. A. Bokach, V. Y. Kukushkin, Coord. Chem. Rev., 2013, 257, 2293-2316.
[66]	A. S. Touchy, K. Kon, W. Onodera, K.-I. Shimizu, Adv. Synth. Catal., 2015, 357, 1499-1506.
[67]	A. Lisovskaya, K. Kanjana, D. M. Bartels, Phys. Chem. Chem. Phys., 2020, 22, 19046-19058.
[68]	W. E. Morgan, J. R. Van Wazer, J. Phys. Chem., 1973, 77, 964-969.
[69]	R. D. Shannon, Acta Crystallogr. A, 1976, 32, 751-767.
[70]	Y. D. Lin, Y. H. Chen, L. T. Qiu, S. H. Zheng, J. Chem. Phys., 2024, 160, 094708.
[71]	M. Yang, S. Li, J. Huang, ACS Appl. Mater. Interfaces, 2021, 13, 39501-39512.
[72]	S. Cheng, J. Wang, S. Duan, J. Zhang, Q. Wang, Y. Zhang, L. Li, H. Liu, Q. Xiao, H. Lin, Chem. Eng. J., 2021, 417, 128172.
[73]	E. Rojas, J. J. Delgado, M. O. Guerrero-Pérez, M. A. Bañares, Catal. Sci. Technol., 2013, 3, 3173.
[74]	K. Ren, F. Jia, C. Zhang, E. Xing, Y. Li, Fuel, 2023, 335, 127047.
[75]	M. Cao, L. Liu, S. Tang, Z. Peng, Y. Wang, Adv. Synth. Catal., 2019, 361, 1887-1895.
[76]	L. E. Stephans, A. Myles, R. R. Thomas, Langmuir, 2000, 16, 4706-4710.
[77]	A. Mekki-Berrada, S. Bennici, J.-P. Gillet, J.-L. Couturier, J.-L. Dubois, A. Auroux, ChemSusChem, 2013, 6, 1478-1489.
[78]	B. Saville, J. Phys. Chem., 1971, 75, 2215-2217.
[79]	M. Liang, Z. Xu, T. Zhou, L. Chen, J. Chen, Green Chem., 2024, 26, 3832-3852.
[80]	Z. Xu, J. Chen, Chem. Eng. J., 2024, 486, 150039.
[81]	Y. Li, C. Yao, X. Wang, J. Chen, Y. Xu, J. Catal., 2025, 442, 115915.
[82]	I. Khan, S. Zaib, S. Batool, N. Abbas, Z. Ashraf, J. Iqbal, A. Saeed, Bioorg. Med. Chem., 2016, 24, 2361-2381.
[83]	Z. A. Mas’ud, N. Darmawan, J. Dawolo, Y. B. Apriliyanto, J. Chem., 2020, 2020, 1092643.
[84]	R. I. S. Romão, A. M. Gonçalves da Silva, Chem. Phys. Lipds., 2004, 131, 27-39.