Enhanced conversion of lignin into mono-cycloalkanes via C-C bonds cleavage over multifunctional Pt-Nb/MOR catalyst

doi:10.1016/S1872-2067(24)60260-3

Abstract

Abstract:

The efficient conversion of lignin into mono-cycloalkanes via both C-O and C-C bonds cleavage are attractive, but challenging due to the high C-C bond dissociation energy. Previous studies have demonstrated that NbO_x-based catalysts exhibited exceptional capabilities for C_Ar-C bond cleavage and broken the limitation of lignin monomers. In this work, we presented an economical multifunctional Pt-Nb/MOR catalyst that achieved an impressive monomer yield of 147% during the depolymerization and hydrodeoxygenation of lignin into mono-cycloalkanes. Reaction pathway studies showed that unlike traditional NbO_x-based catalytic system, bicyclohexane was an important intermediate in this system and followed the C_sp₃-C_sp₃ cleavage pathway after complete cyclic-hydrogenation. Deep investigations demonstrated that the doping of Nb in Pt/MOR not only enhanced the activation of hydrogen by Pt, but also increased the acidity of MOR, both of these are favor for the hydrogenolytic cleavage of C_sp₃-C_sp₃ bonds. This work provides a low-cost catalyst to obtain high-yield monomers from lignin under relatively mild conditions and would help to design catalysts with higher activity for the valorization of lignin.

Key words: Lignin, Mono-cycloalkanes, C-C bond cleavage, Pt-Nb/MOR catalyst

Zhiruo Guo, Xiaohui Liu, Yong Guo, Yanqin Wang. Enhanced conversion of lignin into mono-cycloalkanes via C-C bonds cleavage over multifunctional Pt-Nb/MOR catalyst[J]. Chinese Journal of Catalysis, 2025, 71: 285-296.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60260-3

https://www.cjcatal.com/EN/Y2025/V71/I4/285

Figures/Tables 14

Table 1 Catalytic performance of various 2Pt-2Nb/zeolite catalysts.

Entry	Catalyst	Conversion /%		Yield/%
Entry	Catalyst	Conversion /%	2	3	4	5	6	7	8	9	Monomers
1	2Pt-2Nb/MOR	99.9	—	1.7	4.7	5.1	48.2	8.5	19.1	3.5	75.8
2	2Pt-2Nb/β₄₀	99.9	—	—	3.5	—	38.5	9.6	18.3	—	66.4
3	2Pt-2Nb/β₂₅	99.9	—	—	10.7	—	22.6	2.5	11.8	—	36.9
4	2Pt-2Nb/ZSM-5	56.1	6.6	15.5	5.9	—	19.7	1.0	3.1	1.7	23.8
5	2Pt-2Nb/USY	78.1	2.7	17.5	6.0	1.3	18.4	1.6	4.5	15.2	24.5
6	2Pt/Nb₂O₅	99.9	1.2	24.2	14.6	8.9	29.3	12.5	1.4	0.2	43.2
7	2Pt/NbOPO₄	99.9	1.4	20.1	17.6	7.6	37.1	11.7	1.7	0.4	50.5

Table 2 Catalytic performance of Pt-Nb/MOR catalysts with different metal contents.

Entry	Catalysts	Conversion /%		Yield/%
Entry	Catalysts	Conversion /%	2	3	4	5	6	7	8	9	Monomers
1	2Pt-2Nb	99.9	—	1.7	4.7	5.1	48.2	8.5	19.1	3.5	75.8
2	2Pt	99.9	12.7	10.0	17.9	6.5	20.7	5.2	6.8	13.8	32.7
3	2Pt-1Nb	99.9	2.4	2.7	9.14	4.2	33.4	8.1	11.0	17.9	52.5
4	2Pt-5Nb	99.9	—	3.8	17.6	13.0	30.1	12.9	9.8	7.1	52.8
5	2Pt-10Nb	99.9	—	13.0	12.6	4.1	24.8	15.2	9.6	15.7	49.6
6	1Pt-2Nb	89.4	25.1	20.7	8.1	2.4	12.5	9.0	2.1	4.2	23.6
7	0.5Pt-2Nb	85.5	36.7	9.6	2.4	0.7	8.9	6.8	1.5	11.7	17.2
8	2Nb	25.0	17.9	—	—	—	—	—	—	—	—

Fig. 1. Time course profiles of 1. Reaction conditions: 1.3 mmol 1, 0.05 g 2Pt-2Nb, 5 mL octane, 0.5 MPa H2, 260 °C.

Fig. 2. Conversion and monomer yield when using phenylcyclohexane (3) as substrates over different catalysts. Reaction conditions: 1.3 mmol phenyl-cyclohexane, 0.05 g catalysts, 5 mL octane, 0.5 MPa H2, 260 °C, 1 h.)

Fig. 3. Conversion and monomer yield when using bicyclohexane (4) as substrates over different catalysts. Reaction conditions: 1.3 mmol bicyclohexane, 0.05 g catalysts, 5 mL Octane, 0.5 MPa H2, 260 °C, 1 h. a 0.5 h.

Scheme 1. Proposed reaction pathway for the cleavage of C-C linkage.

Fig. 4. Conversion and monomer yield of model compounds over 2Pt-2Nb. Reaction conditions: 1.3 mmol substrate, 0.05 g catalysts, 5 mL octane, 0.5 MPa H2, 260 °C, 12 h. a 24 h.

Fig. 5. Catalytic performance on lignin over 2Pt-2Nb. Reaction conditions: 0.2 g lignin, 0.2 g 2Pt-2Nb/MOR, 5 mL octane, 0.5 MPa H2, 300 °C, 40 h. a 0.2 g 2Pt/NbOPO4 as catalyst.

Fig. 6. Stability test of 2Pt-2Nb. Reaction conditions: 0.2 g Birch lignin, 0.2 g 2Pt-2Nb/MOR, 5 mL octane, 0.5 MPa H2, 300 °C, 40 h.

Table 3 Metal contents, BET surface area, pore volume, pore size and Pt dispersion of catalysts.

Catalysts	Pt content ^a (wt%)	Nb content ^a (wt%)	A_BET (m²/g)	V_Total (cm³/g)	Average pore size (nm)	Pt dispersion ^b (%)
MOR	—	—	409.6	0.33	3.3	—
2Pt	1.7	—	303.6	0.16	2.1	32.9
2Pt-2Nb	1.7	2.1	395.5	0.21	2.1	30.5
2Pt-2Nb-Reuse 3	1.5	2.0	394.1	0.21	2.1	27.1

Fig. 7. TEM images of 2Pt (a,b) and 2Pt-2Nb (c,d).

Fig. 8. Pt 4d5/2 XPS spectra (a) and CO-DRIFT spectra (b) of 2Pt and 2Pt-2Nb catalysts.

Fig. 9. Reaction order of H2 (a) and bicyclohexane (b) on 2Pt-2Nb. Reaction order of H2 (c) and bicyclohexane (d) on 2Pt.

Fig. 10. Py-IR spectra of MOR, 2Pt and 2Pt-2Nb catalysts at 100 °C.

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