Research Progress in Application of Lignin and Its Derivatives Supported Metal Catalysts in Organic Synthesis

doi:10.6023/cjoc202207013

Abstract

The attention of biomass-based catalysts has been continuously increased due to the proposal of carbon neutralization development concept. The use of lignin as a support for transition metal catalysts for the preparation of heterogeneous catalysts in the field of organic synthesis can greatly improve the utilization value of lignin. The extensive presence of oxygen-containing functionalities in the lignin structure provides a variety of binding sites for the loading of metal catalysts, and metal particles can be efficiently captured by physical adsorption/deposition, ion exchange, and electrostatic complexation with hydroxyl functional groups. The structure of lignin is firstly introduced, and the methods for preparing heterogeneous catalysts are then described. Lignin and its derivatives supported metal catalysts catalyzed Click reaction, Glaser reaction, Huisgen [3＋2] cycloaddition reaction, Heck reaction, Suzuki reaction, Sonogashira reaction, Stille coupling, Michael addition/dehydration tandem, Electrophilic ring-opening reaction, Fridel-Crafts type reaction, ethylene polymerization and other reactions. Thus, at the end of this review, the existing problems and development trends are prospected.

Key words: functionalized lignin, lignin-supported metal catalyst, heterogeneous catalysis, organic synthesis, green chemistry

Cite this article

Baichuan Mo, Chunxia Chen, Jinsong Peng. Research Progress in Application of Lignin and Its Derivatives Supported Metal Catalysts in Organic Synthesis[J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1215-1240.

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Fig. & Tab. 44

Figure 1. Structural unit of lignin

Figure 2. Representative structures of lignin

名称	提取流程	特征
硫酸盐木质素	Na₂S/NaOH	高度修饰, 部分碎片化
木质素磺酸盐	从软木材硫酸盐制浆工艺的废液中提取木质素	高度修饰, 高平均分子量, 醚键断裂, 甲氧基裂解且会形成新的碳-碳键
磨木质素(MWL)	球磨后用二氧六环和水混合溶剂提取	最接近天然结构, 多次球磨可能导致部分解聚
有机溶剂木质素	直接用有机溶剂提取木质素	条件温和, 木质素收率高, 可以回收有机溶剂
离子液体木质素	逐步沉淀或选择性提取	与硫酸盐木质素比结构改变更小, 分子量分布更均匀
蒸汽爆破木质素	对纤维进行高温蒸汽爆破	不需要或需要很少的化学试剂, 能耗低, 处理时间短, 只改变某些特定的官能团
碱性木质素	在碱性条件下处理木质素	通过β-O-4断裂进行部分降解

Table 1. Extraction methods and characteristics of lignin derivatives

Scheme 1. Preparation of DIS@SLS-TMEDA-Cu catalyst

Scheme 2. Mechanism for the Huisgen [3＋2] cycloaddition reaction catalyzed by Cu2O@Lignin

Scheme 3. Preparation of SLS-FAS-Cu catalyst

Scheme 4. Metal nanoparticles supported on the three-dimensional biomass

污染物	还原率/%	时间/min
MO	99.5	4
MB	96.6	5
CR	95.1	7
AO	98.8	14
4-NP	96.8	10

Table 2. Catalytic reduction performance of Cu-ZV-MNPs/EFB for pollutants

Scheme 5. Preparation of Cu(II)-SLS nanoflowers heterogeneous catalyst

Scheme 6. Preparation of Fe3O4-Lignin-Cu NPs catalyst

Scheme 7. Synthesis of Cu NPs@Fe3O4-LS-CS catalyst

Scheme 8. Mechanism of Cu NPs@Fe3O4-LS-CS catalyzed synthesis of 5-aryltetrazoles

Scheme 9. Synthesis process of Cu@MLS-TA

Scheme 10. Proposed mechanism for the N-formylation of amines catalyzed by Cu@MLS-TA

电极	电解液	法拉第效率/%
铜-木质素-泡沫镍	0.1 mol/L Na₂SO₄	23.20
铜-泡沫镍	0.1 mol/L Na₂SO₄	16.50
铜/N-参杂石墨烯	0.1 mol/L KHCO₃	63
铜网	0.5 mol/L KHCO₃	13
3D CuO	0.1 mol/L KHCO₃	13
Cu/TiO₂	0.2 mol/L KI	27.40
石墨烯/Cu₂O	0.5 mol/L NaHCO₃	9.93
Cu₄Zn	0.1 mol/L KHCO₃	29.10

Table 3. Faradaic efficiency of electrochemical reduction of CO2 with different catalysts

Figure 3. Scanning electron microscope micrographs of (a) Cu, (b) Cu-Ni foam, (c) Cu-lignin and (d) Cu-lignin-Ni foam

Scheme 11. Preparation of heterogeneous Fe3O4@LigA/Cu catalyst

Scheme 12. Reduction reaction catalyzed by Fe3O4@LigA/Cu

Entry	Catalyst	Time/h
1	LAC-Pd	4
2	LACT-Pd	2
3	LAC-Pd	2
4	LACT-Pd	2
5	LACT-Pd	2
6	LACT-Pd	2
7	LACT-Pd	2
8	LACT-Pd	2
9	LACT-Pd	6

Table 4. LAC-Pd and LACT-Pd catalyzed hydrogenation of alkenes

Entry	Arylbromide	Arylboronic acid	Cross-coupling	Homo-coupling
1
2				Not detected
3				Not detected

Table 5. LACT-Pd catalyzed Suzuki-Miyaura coupling reaction

Scheme 13. Preparation of three heterogeneous catalysts

Scheme 14. Preparation route of lignin-TEPA-Pd catalyst

Scheme 15. Synthesis of Pd NPs@lignin catalyst

Scheme 16. Cycling experiment of Sonogashira coupling reaction catalyzed by Pd NPs@lignin

Scheme 17. Synthesis of FLA-Pd catalyst

Figure 4. Structural diagram of Pd NPs@Fe3O4-CLS

Scheme 18. Proposed mechanism for synthesis of Pd NPs

Scheme 19. Synthesis of Fe3O4-lignin@Pd NPs

Scheme 20. Mechanism of Mizoroki-Heck reaction catalyzed by Fe3O4-lignin@Pd NPs

Scheme 21. Preperation of Pd@LPR catalyst

Scheme 22. Synthesis of FLT-Pd heterogeneous catalyst

Scheme 23. Synthesis of Ag/C and Ag/C catalyzed reduction of nitrophenol

Scheme 24. Preparation of Ag@SLSPF catalyst

Scheme 25. Preparation of heterogeneous catalyst SLS@Ag

Scheme 26. Preparation procedure of FeC catalyst

Scheme 27. Fe@C catalyzed synthesis of liquid hydrocarbon from biosyngas

Scheme 28. FeNi-CDL catalyzed hydrogenation reduction of nitrobenzene and phenylacetylene

Scheme 29. Preparation of P-(L-FeTPP)

Scheme 30. Preparation of Pt nanoparticles and their catalytic hydrogenation of α-pinene

Scheme 31. Preparation of hollow spherical lignin-supported vanadium-based Ziegler-Natta catalyst and its application in ethylene polymerization

Scheme 32. Synthesis of LCN@Zn-SAC

Scheme 33. Preparation of deprotected lignin-supported Co(II) catalyst

Scheme 34. Preparation of HMFCA and FDCA from HMF catalyzed by DL-CoTCPP

Scheme 35. Degradation of cellulose to HMF and xylan to Furfural by bifunctional lignosulfonate catalysts

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木质素及其衍生物负载金属催化剂在有机合成中的应用研究进展