Highly dispersed Pd nanoparticles <i>in situ</i> reduced and stabilized by nitrogen-alkali lignin-doped phenolic nanospheres and their application in vanillin hydrodeoxygenation

doi:10.1007/s11705-024-2478-1

2024, Vol. 18

Issue (11) : 127 https://doi.org/10.1007/s11705-024-2478-1

Highly dispersed Pd nanoparticles in situ reduced and stabilized by nitrogen-alkali lignin-doped phenolic nanospheres and their application in vanillin hydrodeoxygenation

Xue Gu, Yu Qin, Jiahui Wei, Bing Yuan(

), Fengli Yu, Liantao Xin, Congxia Xie, Shitao Yu(

)

State Key Laboratory Base of Eco-chemical Engineering, College of Chemistry and Molecular Engineering, College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

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Abstract

Herein, we introduced a nitrogen-alkali lignin-doped phenolic resin (N@AL_nPR) to produce palladium nanoparticles through an in situ reduction of palladium in an aqueous phase, without the need for additional reagents or a reducing atmosphere. The phenolic resin nanospheres and the resulting palladium nanoparticles were extensively characterized. Alkali lignin created a highly conducive environment for nitrogen incorporation, dispersion, reduction, and stabilization of palladium, leading to a distinct catalytic performance of palladium nanoparticles in vanillin hydrodeoxygenation. Under specific conditions of 1 mmol of vanillin, 40 mg of catalyst, 1 MPa H₂, 90 °C, and 3 h, the optimized Pd/N@AL₃₀PR catalyst exhibited a nearly complete conversion of vanillin, 98.9% selectivity toward p-creosol, and good stability for multiple reuses. Consequently, an environmentally friendly lignin-based catalyst was developed and used for the efficient hydrodeoxygenation conversion of lignin-based platform compounds.

Keywords alkali lignin phenolic nanosphere palladium nanoparticles hydrodeoxygenation vanillin

Corresponding Author(s): Bing Yuan,Shitao Yu

Just Accepted Date: 21 May 2024 Issue Date: 24 July 2024

Cite this article:

Xue Gu,Yu Qin,Jiahui Wei, et al. Highly dispersed Pd nanoparticles in situ reduced and stabilized by nitrogen-alkali lignin-doped phenolic nanospheres and their application in vanillin hydrodeoxygenation[J]. Front. Chem. Sci. Eng., 2024, 18(11): 127.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2478-1
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I11/127

Fig.1 SEM images of (a) N@AL₀PR, (b) N@AL₁₀PR, (c) N@AL₃₀PR, and (d) N@AL₄₀PR. The inset shows the particle size distribution of different resin spheres.

Fig.2 Typical HAADF-STEM images of (a) Pd/N@AL₀PR and (b) Pd/N@AL₃₀PR, (c) HRTEM image of Pd/N@AL₃₀PR, and (d) N₂ adsorption/desorption isotherms of N@AL_nPR microspheres. The inset shows the Pd particle size distribution of different catalysts.

Entry	Catalyst	Conv. of vanillin/%	Sel. of product/%
Entry	Catalyst	Conv. of vanillin/%	p-Creosol	Vanillyl alcohol
1	Pd/N@AL₀PR	74.6	51.4	48.6
2	Pd/N@AL₁₀PR	98.5	89.3	10.7
3	Pd/N@AL₃₀PR	99.8	92.7	7.3
4	Pd/N@AL₄₀PR	98.9	88.3	11.7
5	Pd/N@SLS₃₀PR	97.5	92.5	7.5
6	Pd/AL₃₀PR	79.0	59.5	40.5
7	Pd'/N@AL₃₀PR^a)	98.5	90.3	9.7
8	Pd"/N@AL₃₀PR^b)	98.7	92.1	7.9
9	Pd/N@C_AL30PR^c)	48.1	73.4	26.6
10	$P d N a B H 4$ /N@C_AL30PR^d)	97.0	93.9	6.1

Tab.1 Effect of raw materials on the preparation of Pd nanoparticles reduced and stabilized by phenolic spheres*

Fig.3 The corresponding EDS elemental mapping images of (a–e) Pd/N@AL₃₀PR and (f–j) Pd/N@AL₀PR.

Fig.4 FT-IR spectra of AL, AL₃₀PR, N@AL₀PR, N@AL₃₀PR, and Pd/N@AL₃₀PR.

Fig.5 XRD patterns of N@AL₀PR, N@AL₃₀PR, and Pd/N@AL₃₀PR.

Fig.6 (a) XPS full-scan spectra, (b) Pd 3d fitted spectra, (c) N 1s fitted spectra, and (d) C 1s fitted spectra of different samples.

Tab.2 Effect of preparation conditions of Pd/N@AL₃₀PR^a)

Fig.7 Effect of (a, b) Pd/N@AL₃₀PR dosage (conditions: 1 mmol vanillin, 10 mL water, 80 °C, 1 MPa H₂); (c, d) reaction temperature (conditions: 40 mg Pd/N@AL₃₀PR, 1 mmol vanillin, 10 mL water, 1 MPa H₂); (e, f) reaction pressure (conditions: 40 mg Pd/N@AL₃₀PR, 1 mmol vanillin, 10 mL water, 90 °C) in vanillin hydrodeoxygenation.

Fig.8 Plausible mechanism of catalytic hydrodeoxygenation of vanillin over Pd/N@AL₃₀PR.

Fig.9 Catalytic stability of Pd/N@AL₃₀PR in vanillin hydrodeoxygenation. Reaction conditions: 40 mg of Pd/N@AL₃₀PR, 1 mmol of vanillin, 10 mL of water, 80 °C, 1 MPa H₂, 4 h.

Fig.10 (a) HAADF-STEM, (b) XPS scan spectrum, (c) N 1s fitted spectrum, and (d) Pd 3d fitted spectrum of Pd/N@AL₃₀PR*, the spent catalyst sample after 6 runs. The inset shows the Pd particle size distribution of the spent catalyst.

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