Geometric and electronic effects on the performance of a bifunctional Ru2P catalyst in the hydrogenation and acceptorless dehydrogenation of N-heteroarenes

doi:10.1016/S1872-2067(20)63747-0

Abstract

Abstract:

The development of bifunctional catalysts for the efficient hydrogenation and acceptorless dehydrogenation of N-heterocycles is a challenge. In this study, Ru₂P/AC effectively promoted reversible transformations between unsaturated and saturated N-heterocycles affording yields of 98% and 99%, respectively. Moreover, a remarkable enhancement in the reusability of Ru₂P/AC was observed compared with other Ru-based catalysts. According to density functional theory calculations, the superior performance of Ru₂P/AC was ascribed to specific synergistic factors, namely geometric and electronic effects induced by P. P greatly reduced the large Ru-Ru ensembles and finely modified the electronic structures, leading to a low reaction barrier and high desorption ability of the catalyst, further boosting the hydrogenation and acceptorless dehydrogenation processes.

Key words: Ruthenium phosphide, Bifunction catalyst, Reaction mechanism, Geometric and electronic effects, Hydrogenation, Acceptorless dehydrogenation

Fangjun Shao, Zihao Yao, Yijing Gao, Qiang Zhou, Zhikang Bao, Guilin Zhuang, Xing Zhong, Chuan Wu, Zhongzhe Wei, Jianguo Wang. Geometric and electronic effects on the performance of a bifunctional Ru₂P catalyst in the hydrogenation and acceptorless dehydrogenation of N-heteroarenes[J]. Chinese Journal of Catalysis, 2021, 42(7): 1185-1194.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63747-0

https://www.cjcatal.com/EN/Y2021/V42/I7/1185

Figures/Tables 10

Scheme 1. Schematic of the Ru2P/AC preparation process along with the hydrogenation and dehydrogenation of quinolines based on Ru2P/AC.

Fig. 1. (a) TEM image, inset shows the size distribution histogram; (b) HRTEM image; (c) Corresponding EDS elemental (C, P, and Ru) mapping, and (d) Elemental line profile of Ru and P.

Table 1 Reversible transformation between 1a and 2a via hydrogenation-acceptorless dehydrogenation reactions catalyzed by a variety of catalysts.


Entry	Catalyst	Hydrogenation ^a			Dehydrogenation ^b
Entry	Catalyst	Conversion (%)	Selectivity ^c (%)	TOF ^d(h^‒1)	Conversion (%)	Selectivity ^e(%)	TOF ^f(h^-1)
1	Ru₂P/AC	98.7	>99.9	164.4	98.0	>99.9	22.5
2	AC	0.0	0.0	—	0.0	0.0	—
3	P_AC	0.0	0.0	—	62.9	>99.9	—
4	P/AC	0.0	0.0	—	0.0	0.0	—
5	Ru/AC	65.7	98.9	47.3	47.9	99.2	2.2
6	Ru/P_AC	5.9	98.1	3.64	61.4	99.3	2.8
7	RuO₂/AC	0.0	0.0	—	99.2	>99.9	4.6
8	RuS₂/AC	32.6	99.6	19.8	99.7	94.6	4.5

Fig. 2. (a) XPS spectrum of Ru 3p3/2 and Ru 3p1/2; (b) XPS spectrum of P 2p.

Fig. 3. (a?d) Charge density difference of the product of hydrogenation (2a) on Ru(101), RuS2(200), RuO2(110), and Ru2P(112), respectively, and (e?h) Charge density difference of the product of dehydrogenation (1a) on Ru(101), RuS2(200), RuO2(110), and Ru2P(112), respectively.

Fig. 4. (a) 2-D activity heat map displaying the hydrogenation reaction conversion rate of various catalysts as a function of the desorption energy and rate-determining step barrier of 2a. Hydrogenation conditions: 0.5 mmol quinoline, 15 mg Ru2P/AC catalyst, H2 (5 bar), EtOH 2 mL at 60 °C for 2 h. (b) 2-D activity heat map displaying the dehydrogenation reaction conversion rate of various catalysts as a function of the rate-determining step barrier and desorption energy of 1a. Dehydrogenation conditions: 0.25 mmol tetrahydroquinoline, 20 mg Ru2P/AC catalyst, N2 (1 bar), 3 mL mesitylene at 145 °C for 10 h.

Fig. 5. (a) Energy profiles of C9H7N hydrogenation; (b) Energy profiles of C9H11N dehydrogenation in the presence of Ru2P (112), Ru (101), RuS2 (200), and RuO2 (110).

Fig. 6. Reusability test of the catalyst: (a) reusability test for the hydrogenation by the Ru2P/AC catalyst over 8 cycles at 60 °C for 5 h under H2 (5 bar); (b) reusability test for the hydrogenation by comparative catalysts over 5 cycles: Ru/AC was used at 80 °C for 5 h under H2 (10 bar), while RuS2/AC was used at 80 °C for 12 h under H2 (10 bar); (c) reusability test for the dehydrogenation by the Ru2P/AC catalyst over 8 cycles at 145 °C for 24 h under N2 (1 bar); (d) reusability test for the dehydrogenation by the Ru/AC and RuS2/AC catalysts over 5 cycles at 145 °C for 24 h under N2 (1 bar).

Table 2 Ru2P/AC catalyzed hydrogenation and dehydrogenation of various quinolines.


Entry	Substrate (A)	Substrate (B) ^a	Hydrogenation ^b		Dehydrogenation ^c
Entry	Substrate (A)	Substrate (B) ^a	Conversion (%)	Selectivity ^d(%)	Conversion (%)	Selectivity ^e(%)
1			98.7	>99.9	98.0	>99.9
2			99.1	>99.9	99.9	92.5
3			99.5	>99.9	99.9	86.8
4			99.4	>99.9	99.9	93.4
5			98.9^f	>99.9	99.9	95.8
6			99.2	>99.9	99.9	98.0
7			99.6	>99.9	99.9	89.9
8			99.2	>99.9	99.9	87.6
9			99.5^g	>99.9	99.0	89.4

Table 3 Hydrogenation of quinoxaline: molecular coupling experiments a.


Entry	H₂ pressure (bar)	Time (h)	Conversion (%)	Selectivity ^b (%)
Entry	H₂ pressure (bar)	Time (h)	Conversion (%)	4a	5a
1	—	12	0	—	—
2	5	5	12.4	6.5	3.7
3	10	5	16.3	9.1	6.1
4	10	10	16.7		16.4
5	N₂	12	0	—	—

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Geometric and electronic effects on the performance of a bifunctional Ru₂P catalyst in the hydrogenation and acceptorless dehydrogenation of N-heteroarenes

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