In-situ Synthesis of Nitrogen-doped Graphene Layer Encapsulated Palladium Nanoparticles for Highly Selective Hydrogenation of Vanillin

doi:10.6023/A22120481

Abstract

As the only natural and sustainable carbon source, biomass shows great potential in solving current environmental and energy problems and creating a carbon-neutral society. Selective hydrogenation is a kind of important reaction. Various unsaturated functional groups in biomass are typical targets of selective hydrogenation. Therefore, selectivity is the key index to measure the efficiency of the hydrogenation reaction. Vanillin is an important platform compound in biomass conversion. In recent years, selective hydrogenation of vanillin to biofuels and other high-value-added chemicals has received widespread attention. Because vanillin has different reducible functional groups (aldehyde group, methoxy group, and hydroxyl group), it is very important to control the selectivity of vanillin hydrogenation. Vanillyl alcohol has long-lasting sweetness and nutty aromas and is used in the food and perfume industries. 2-Methoxy-4-methylphenol (MMP) is also an important biofuel. Therefore, selective hydrogenation of vanillin to vanillyl alcohol or MMP is an important synthesis route. Here, we propose a strategy to introduce the chemical active center of catalytic reaction and the anchoring center of metal nanoparticle deposition by doping nitrogen atoms of graphene, which makes the application of graphene in hydrogenation catalysis obtain better performance. In this work, we report a simple method for in-situ synthesis of nitrogen-doped graphene-supported palladium nanoparticles Pd@N/C-2 catalyst and its application in selective hydrogenation of the C=O bond. The prepared catalyst has good catalytic activity and product selectivity for the hydrogenation of vanillin and has the advantages of simple preparation, high activity and stable performance. It is easy to be separated from organic reaction conditions and can be reused many times. Under relatively mild reaction conditions, Pd@N/C-2 catalyzed the complete conversion of vanillin to vanillyl alcohol and MMP, and the yields were 89% and 99%, respectively. It is worth noting that through the regulation of solvents, we achieved highly selective hydrogenation of vanillin to vanillyl alcohol and MMP, respectively.

Key words: vanillin, vanillyl alcohol, 2-methoxy-4-methylphenol, homogeneous catalyst, selective hydrogenation

Cite this article

Bin Xu, Xiuzhi Wei, Jiangmin Sun, Jianguo Liu, Longlong Ma. In-situ Synthesis of Nitrogen-doped Graphene Layer Encapsulated Palladium Nanoparticles for Highly Selective Hydrogenation of Vanillin[J]. Acta Chimica Sinica, 2023, 81(3): 239-245.

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Fig. & Tab. 8

Figure 1. Representative SEM images of Pd@N/C-2 (a), Pd@N/C-9 (b), purchased Pd@N/C (c); representative HAADF-TEM images of Pd@N/C-2 (d, g), Pd@N/C-9 (e), purchased Pd@N/C (f); EDS elemental mapping of Pd@N/C-2 (h)

Figure 2. XRD patterns of Pd@N/C-2, Pd@N/C-9 and purchased Pd@N/C

Figure 3. N2 adsorption-desorption isotherms of Pd@N/C-2

Figure 4. XPS spectra of Pd@N/C-2

Figure 5. Effects of (a) solvent, (b) temperature, (c) pressure and (d) time on the selective hydrogenation of benzaldehyde catalyzed by Pd@N/C-2

Entry	Condition	Conversion^b/%	Selectivity^b/%
1	Standard condition	92.8	93.4
2	N₂	trace	trace
3	No catalyst	trace	trace
4	Purchased Pd@C	>99	trace
5	Purchased Pd@N/C	11.3	65.4
6	Pd@N/C-9	79.7	85.6

Table 1. Control experiments for selective hydrogenation of benzaldehyde

Entry	Conversion^b/%	Selectivity^b/%
1	96.1	97.4
2	>99	98.0
3	97.5	96.2
4	85.9	95.3
5	>99	93.3
6	84.4	86.4
7^c	78.7	>99

Table 2. Hydrogenation reduction of various aldehyde by catalyst Pd@N/C-2

Figure 6. Optimization of reaction conditions for hydrogenation of vanillin (a) and cycle performance (b) of Pd@N/C-2 catalyst

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