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

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.

Key words： alkali lignin; phenolic nanosphere; palladium nanoparticles; hydrodeoxygenation; vanillin

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 31870554 and 32071710).

References

1 Erythropel H C , Zimmerman J B , de Winter T M , Petitjean L , Melnikov F , Lam C H , Lounsbury A W , Mellor K E , Janković N Z , Tu Q . . The Green ChemisTREE: 20 years after taking root with the 12 principles. Green Chemistry, 2018, 20(9): 1929–1961

2 Liu Z H , Li B Z , Yuan J S , Yuan Y J . Creative biological lignin conversion routes toward lignin valorization. Trends in Biotechnology, 2022, 40(12): 1550–1566

3 Sivagurunathan P , Raj T , Mohanta C S , Semwal S , Satlewal A , Gupta R P , Puri S K , Ramakumar S S V , Kumar R . 2G waste lignin to fuel and high value-added chemicals: approaches, challenges and future outlook for sustainable development. Chemosphere, 2021, 268: 129326

4 Gan M J , Niu Y Q , Qu X J , Zhou C H . Lignin to value-added chemicals and advanced materials: extraction, degradation, and functionalization. Green Chemistry, 2022, 24(20): 7705–7750

5 Zhang L , Shang N , Gao S , Wang J , Meng T , Du C , Shen T , Huang J , Wu Q , Wang H . . Atomically dispersed Co catalyst for efficient hydrodeoxygenation of lignin-derived species and hydrogenation of nitroaromatics. ACS Catalysis, 2020, 10(15): 8672–8682

6 Xu L , Liaqat F , Sun J , Khazi M I , Xie R , Zhu D . Advances in the vanillin synthesis and biotransformation: a review. Renewable & Sustainable Energy Reviews, 2024, 189: 113905

7 Zhai Y , Chu M , Shang N , Wang C , Wang H , Gao Y . Bimetal Co₈Ni₂ catalyst supported on chitin-derived N-containing carbon for upgrade of biofuels. Applied Surface Science, 2020, 506: 144681

8 RanJYangChengRCuiYWangJ. YangCheng R, Cui Y, Wang J. Significant promotion of carboxyl groups in palladium nanoparticles-supported biomass carbon catalysts for efficient low-temperature hydrodeoxygenation of lignin derivatives in water. ACS Sustainable Chemistry & Engineering, 2022, 10(22): 7277–7287

9 Phan D P , Lee E Y . Phosphoric acid enhancement in a Pt-encapsulated metal-organic framework (MOF) bifunctional catalyst for efficient hydro-deoxygenation of oleic acid from biomass. Journal of Catalysis, 2020, 386: 19–29

10 Fan H , Qin F , Yuan Q , Sun Z , Gu H , Xu W , Tang H , Liu S , Wang Y , Chen W . . Improving the selectivity of hydrogenation and hydrodeoxygenation for vanillin by using vacancy-coupled Ru-N₃ single atoms immobilized on defective boron nitride. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2023, 11(33): 17560–17569

11 Yue X , Shang N , Gao W , Cheng X , Gao S , Wang C , Wang Z . PdAg nanoparticles supported on bipyridine-based porous organic polymers: an effective bimetallic catalyst for the hydrodeoxygenation of vanillin. Energy Technology, 2021, 9(9): 2100306

12 Santos J L , Mäki-Arvela P , Wärnå J , Monzón A , Centeno M A , Murzin D Y U . Hydrodeoxygenation of vanillin over noble metal catalyst supported on biochars. Part II: catalytic behaviour. Applied Catalysis B: Environmental, 2020, 268: 118425

13 Zong R , Li H , Ding W , Huang H . Highly dispersed Pd on zeolite/carbon nanocomposites for selective hydrodeoxygenation of biomass-derived molecules under mild conditions. ACS Sustainable Chemistry & Engineering, 2021, 9(29): 9891–9902

14 Strapasson G B , Sousa L S , Báfero G B , Leite D S , Moreno B D , Rodella C B , Zanchet D . Acidity modulation of Pt-supported catalyst enhances C–O bond cleavage over acetone hydrodeoxygenation. Applied Catalysis B: Environmental, 2023, 335: 122863

15 Aadil K R , Barapatre A , Meena A S , Jha H . Hydrogen peroxide sensing and cytotoxicity activity of acacia lignin stabilized silver nanoparticles. International Journal of Biological Macromolecules, 2016, 82: 39–47

16 Chen X , Yuan B , Yu F , Liu Y , Xie C , Yu S . Hydrogenation of α-pinene over platinum nanoparticles reduced and stabilized by sodium lignosulfonate. ACS Omega, 2020, 5(15): 8902–8911

17 Zhang Z , Wei J , Yuan B , Yu F , Xie C , Yu S . Hydrodeoxygenation of vanillin over Pd nanoparticles reduced and stabilized by sodium lignosulfonate in aqueous phase. Industrial Crops and Products, 2023, 192: 116055

18 Pletzer D , Asnis J , Slavin Y N , Hancock R E W , Bach H , Saatchi K , Häfeli U O . Rapid microwave-based method for the preparation of antimicrobial lignin-capped silver nanoparticles active against multidrug-resistant bacteria. International Journal of Pharmaceutics, 2021, 596: 120299

19 Kalami S , Arefmanesh M , Master E , Nejad M . Replacing 100% of phenol in phenolic adhesive formulations with lignin. Journal of Applied Polymer Science, 2017, 134(30): 45124

20 Li J , Zhang J , Zhang S , Gao Q , Li J , Zhang W . Alkali lignin depolymerization under eco-friendly and cost-effective NaOH/urea aqueous solution for fast curing bio-based phenolic resin. Industrial Crops and Products, 2018, 120: 25–33

21 Kalami S , Chen N , Borazjani H , Nejad M . Comparative analysis of different lignins as phenol replacement in phenolic adhesive formulations. Industrial Crops and Products, 2018, 125: 520–528

22 Van Nieuwenhove I , Renders T , Lauwaert J , De Roo T , De Clercq J , Verberckmoes A . Biobased resins using lignin and glyoxal. ACS Sustainable Chemistry & Engineering, 2020, 8(51): 18789–18809

23 Li W , Sun H , Wang G , Sui W , Dai L , Si C . Lignin as a green and multifunctional alternative to phenol for resin synthesis. Green Chemistry, 2023, 25(6): 2241–2261

24 Mennani M , Kasbaji M , Ait Benhamou A , Boussetta A , Mekkaoui A A , Grimi N , Moubarik A . Current approaches, emerging developments and functional prospects for lignin-based catalysts—a review. Green Chemistry, 2023, 25(8): 2896–2929

25 Yang J , Xiong F , Wang H , Ma B , Guo F , Qing Y , Chu F , Wu Y . Facile and scalable construction of nitrogen-doped lignin-based carbon nanospheres for high-performance supercapacitors. Fuel, 2023, 343: 128007

26 Chen S , Wang G , Sui W , Parvez A M , Si C . Synthesis of lignin-functionalized phenolic nanosphere supported Ag nanoparticles with excellent dispersion stability and catalytic performance. Green Chemistry, 2020, 22(9): 2879–2888

27 Chen S , Wang G , Sui W , Parvez A M , Dai L , Si C . Novel lignin-based phenolic nanosphere supported palladium nanoparticles with highly efficient catalytic performance and good reusability. Industrial Crops and Products, 2020, 145: 112164

28 Chen S , Wang G , Pang T , Sui W , Chen Z , Si C . Green assembly of high-density and small-sized silver nanoparticles on lignosulfonate-phenolic resin spheres: focusing on multifunction of lignosulfonate. International Journal of Biological Macromolecules, 2021, 166: 893–901

29 Meng Y , Li C , Liu X , Lu J , Cheng Y , Xiao L P , Wang H . Preparation of magnetic hydrogel microspheres of lignin derivate for application in water. Science of the Total Environment, 2019, 685: 847–855

30 Liu J , Qiao S Z , Liu H , Chen J , Orpe A , Zhao D , Lu G Q M . Extension of the Stöber method to the preparation of monodisperse resorcinol-formaldehyde resin polymer and carbon spheres. Angewandte Chemie, 2011, 123(26): 6069–6073

31 Zhao J , Niu W , Zhang L , Cai H , Han M , Yuan Y , Majeed S , Anjum S , Xu G . A template-free and surfactant-free method for high-yield synthesis of highly monodisperse 3-aminophenol–formaldehyde resin and carbon nano/microspheres. Macromolecules, 2013, 46(1): 140–145

32 Gao S , Zhang Z , Liu K , Dong B . Direct evidence of plasmonic enhancement on catalytic reduction of 4-nitrophenol over silver nanoparticles supported on flexible fibrous networks. Applied Catalysis B: Environmental, 2016, 188: 245–252

33 Pan H , Sun G , Zhao T . Synthesis and characterization of aminated lignin. International Journal of Biological Macromolecules, 2013, 59: 221–226

34 Horikawa Y , Hirano S , Mihashi A , Kobayashi Y , Zhai S , Sugiyama J . Prediction of lignin contents from infrared spectroscopy: chemical digestion and lignin/biomass ratios of cryptomeria japonica. Applied Biochemistry and Biotechnology, 2019, 188(4): 1066–1076

35 Chen Y , Gong X , Yang G , Li Q , Zhou N . Preparation and characterization of a nanolignin phenol formaldehyde resin by replacing phenol partially with lignin nanoparticles. RSC Advances, 2019, 9(50): 29255–29262

36 Carter C F , Lange H , Ley S V , Baxendale I R , Wittkamp B , Goode J G , Gaunt N L , React I R . Flow Cell: a new analytical tool for continuous flow chemical processing. Organic Process Research & Development, 2010, 14(2): 393–404

37 Baran T , Sargin I . Green synthesis of a palladium nanocatalyst anchored on magnetic lignin-chitosan beads for synthesis of biaryls and aryl halide cyanation. International Journal of Biological Macromolecules, 2020, 155: 814–822

38 Kar A K , Sarkar R , Manal A K , Kumar R , Chakraborty S , Ahuja R , Srivastava R . Unveiling and understanding the remarkable enhancement in the catalytic activity by the defect creation in UIO-66 during the catalytic transfer hydrodeoxygenation of vanillin with isopropanol. Applied Catalysis B: Environmental, 2023, 325: 122385

39 Li T , Li H , Li C . Hydrodeoxygenation of vanillin to creosol under mild conditions over carbon nanospheres supported palladium catalysts: influence of the carbon defects on surface of catalysts. Fuel, 2022, 310: 122432

40 Kim H , Yang S , Lim Y H , Ha J M , Kim D H . Upgrading bio-oil model compound over bifunctional Ru/HZSM-5 catalysts in biphasic system: complete hydrodeoxygenation of vanillin. Journal of Hazardous Materials, 2022, 423: 126525