Efficient hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Ni-C3N4 catalysts with ultra-low Ni loading

doi:10.1016/S1872-2067(24)60017-3

Abstract

Abstract:

Selective hydrogenolysis of biomass-based platform compounds is of great importance for the production of chemicals and fuels. Herein, we reported that the catalyst of Ni-C₃N₄ supported on H₂ activated carbon (HC) synthesized by a simple coordination-impregnation-pyrolysis method is efficient for the hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF); the yield of 94.2% can be obtained in a batch reactor and the lifetime of greater than 120 h can be achieved in fixed-bed experiment. It is demonstrated that Ni nanoparticles coated by graphitic C₃N₄ shell were highly dispersed on the surface of HC and the Ni loading is as low as 0.86 wt%, beneficial to the anti-sintering of Ni nanoparticles during the reaction. Both XPS characterizations and theoretical calculations reveal that Ni₃N is the intrinsic active component for the hydrogenolysis, which exhibits efficient activity for the dissociation of C‒O bond. This work opens up a new avenue to develop catalysts with single non-noble metal component for the efficient conversion of biomass-based chemicals.

Key words: Biomass, 5-Hydroxymethylfurfural, 2,5-Dimethylfuran, Hydrogenolysis, Ni₃N

Hongyu Qu, Wende Hu, Xiangcheng Li, Rui Xu, Xiao Han, Junjie Li, Yiqing Lu, Yingchun Ye, Chuanming Wang, Zhendong Wang, Weimin Yang. Efficient hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Ni-C₃N₄ catalysts with ultra-low Ni loading[J]. Chinese Journal of Catalysis, 2024, 60: 253-261.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60017-3

https://www.cjcatal.com/EN/Y2024/V60/I5/253

Figures/Tables 7

Table 1 Hydrogenolysis of HMF to DMF over various catalysts a.

Entry	Catalyst	HMF Conv. (mol%)	Product selectivity (mol%)						Carbon balance (%) ^c
Entry	Catalyst	HMF Conv. (mol%)	DMF	MF	MFA	DHMF	THFDM	Others ^b	Carbon balance (%) ^c
1	Ni-C₃N₄/HC	>99	94.2	3.1	0	0	1.9	0.5	99.7
2	Ni-C₃N₄/C	>99	87.3	0.2	0.2	0	1.4	4.3	93.4
3	Ni/HC	57.4	47.3	43.3	1.2	0.7	1.5	2.1	96.1
4	Ni/HC ^d	98.8	81.6	1.7	0.1	0.1	3.9	3.7	91.1
5	Ni-C₃N₄	9.7	0	19.6	0	69.3	0	2.0	90.9

Scheme 1. Possible reaction pathway for the hydrogenation of HMF.

Fig. 1. TEM (a), HAADF-STEM (b,d), particle size distribution (c) and the corresponding EDX mapping images (e) of Ni-C3N4/HC sample after reduction at 500 °C.

Fig. 2. XPS spectra in Ni 2p3/2 region of Ni-C3N4/HC (a), Ni-C3N4/C (b), Ni/HC-unreduced (c) and Ni/HC (d) samples.

Fig. 3. (a) Adsorption structures and energies of HMF on Ni(111), Ni3N(11-0) and NiO(110) (associative and dissociative) surfaces. (b) Energy profiles of HMF hydrogenation to DMF on Ni3N(11-0) surface at 0 K. (c) Optimized structures of key intermediates and transition states during the hydrogenolysis of HMF to DMF on Ni3N(11-0) surface.

Fig. 4. The reusability of Ni-C3N4/HC catalyst for the conversion of HMF. (a) Reaction conditions in batch reactor: HMF 0.1 g, Ni-C3N4/HC catalyst 0.1 g, THF 20 g, 190 °C, H2 1.5 Mpa, 4 h. (b) Reaction conditions in fixed-bed reactor: 0.5 wt% HMF in THF, Ni-C3N4/HC catalyst 2.75 g, 160 °C, H2 1.5 Mpa, WHSV = 9.7 h?1, gas flow rate 20 mL min?1.

Table 2 Hydrogenolysis of different lignin-derived species catalyzed by Ni-C3N4/HC.

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Efficient hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Ni-C₃N₄ catalysts with ultra-low Ni loading

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