Transition-metals photocatalysts for lignin valorization toward sustainable biofuel production

doi:10.1016/S1872-2067(26)65105-4

Chinese Journal of Catalysis ›› 2026, Vol. 88: 35-85.DOI: 10.1016/S1872-2067(26)65105-4

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Transition-metals photocatalysts for lignin valorization toward sustainable biofuel production

Wenmin Lei^a, Yan Zhang^a, Dalin Sun^a, Lin Ban^a, Heng Zhou^a, Song Yang^a^,^*(), Liquan Jing^b^,^*(), Jinguang Hu^c^,^*(), Heng Zhang^a^,^*()

^a State Key Laboratory of Green Pesticide, State-Local Joint Laboratory for Comprehensive Utilization of Biomass, Center for R&D of Fine Chemicals of Guizhou University, Guiyang 550025, Guizhou, China
^b Key Laboratory of Bio-based Material Science & Technology, Material Science and Engineering College, Northeast Forestry University, Harbin 150040, Heilongjiang, China
^c Department of Chemical and Petroleum Engineering, University of Calgary, 2500 University Drive, NW, Calgary, Alberta T2N1N4, Canada

Received:2025-12-11 Accepted:2026-01-30 Online:2026-09-18 Published:2026-09-05
About author:Song Yang is a distinguished professor at Guizhou University, China. He obtained his Ph.D. from Guizhou University in 2005 and accepted a postdoctoral position in the University of Texas Southwestern Medical Center at Dallas, USA. He was awarded with China National “Ten-Thousand-Talent Plan” and Distinguished Professor of Cheung Kong Scholars Program. His research interests include biofuels, discovery of new agrochemicals, and nanomaterials. He has authored over 50 patents and more than 300 scientific papers in international journals (H-index: 79). He is currently editor-in-chief of Current Catalysis and associate editor of Current Nanoscience.
Liquan Jing (School of Materials Science and Engineering, Northeast Forestry University) obtained a bachelor's degree in 2014 and a doctoral degree in 2021, both from Jiangsu University. From 2021 to 2025, he was a postdoctoral researcher at the Department of Chemistry and Petroleum Engineering at the University of Calgary, under the supervision of Prof. Jinguang Hu and Prof. Ian D. Gates. In early 2025, he joined the School of Materials Science and Engineering at Northeast Forestry University as a professor. His current research interests focus on designing and synthesizing multifunctional photocatalysts for sustainable hydrogen production, converting biomass into high-value bio-products, and methane conversion. He has published over 70 peer-reviewed papers.
Jinguang Hu (Schulich School of Engineering, University of Calgary, Canada) received his Ph.D. degree in the University of British Columbia in 2014. After a postdoctoral fellow during 2014-2017, he moved to the University of Calgary as assistant professor in 2018. He is currently an Associate Professor and Schulich Research Chair in Chemical and Petroleum Engineering at the University of Calgary. He leads “Biomass and Biorefinery Research Lab” and his current research interests focus on biomass valorization, sustainable energy, biofuels and biochemicals, bioinspired materials/systems, and integrated agri-food-energy systems. He has co-authored over 300 peer-reviewed papers, and received numerous prestigious awards, including election to the Royal Society of Canada’s College of New Scholars, the CSChE Bao and Zhu Innovation Award, the CSChE Lectureship Award, the S.C. Trindade Award for Biofuels Research, and the Schulich Early Research Excellence Award. He serves on the External Advisory Board of the Canada Biomass Energy Network, am a member of the China-Canada Joint Centre for BioEnergy, and a Research Fellow of the Grizzly Bear Institute of Canada.
Heng Zhang is Professor at the State-Local Joint Laboratory for Comprehensive Utilization of Biomass of Guizhou University. His research focuses on the controllable preparation of functional catalytic materials for heterogeneous photo/electro/thermal catalysis in biomass transformation. At present, he has published >100 papers (H-index: 47). He received the Guizhou Provincial Natural Science Award (first prize), Wiley China Excellent Author Program, and Elsevier-Stanford University list of world's 2% most-cited scientists. Currently, he is associate editor of Frontiers in Chemistry and editorial board member of several international journals.
Supported by:
The National Natural Science Foundation of China(32302418);The Guizhou Provincial S&T Innovation Platform Research Program(CXPTXM[2025]012);The Central Government Guides Local Science and Technology Development Fund Projects(黔科合中引地(2024)007)

Abstract

Abstract:

Lignin, one of the most abundant and renewable components of biomass, represents a promising feedstock for sustainable biofuel production. Photocatalytic conversion offers an efficient, environmentally benign, and mild route for lignin depolymerization. Transition-metal-based photocatalysts, in particular, enable precise modulation of photogenerated charge carriers and the creation of highly active catalytic sites, thereby facilitating selective lignin transformation while preserving its valuable aromatic motifs. Despite rapid advances, comprehensive reviews on transition metal-based photocatalysts for lignin-to-fuel conversion remain limited. This review systematically summarizes recent progress in transition-metal-based photocatalytic lignin valorization for both gaseous fuels and liquid fuel precursors. We analyze the key bond-cleavage mechanisms using lignin model compounds, uncovering structure-activity relationships between transition-metal catalysts design and lignin depolymerization behavior, and highlight the current challenges hindering practical applications. Furthermore, the synergistic interactions between photocatalytic routes to liquid and gaseous fuels are discussed. Finally, strategies for upgrading lignin-derived intermediates into usable fuels are evaluated, with attention to their technical, economic, and environmental feasibility. Overall, this review offers new insights and theoretical guidance for advancing transition metal-based photocatalytic systems toward efficient and sustainable lignin-to-biofuel conversion.

Key words: Lignin, Photocatalysis, Transition metals, Fuel precursor, Gaseous fuel

Wenmin Lei, Yan Zhang, Dalin Sun, Lin Ban, Heng Zhou, Song Yang, Liquan Jing, Jinguang Hu, Heng Zhang. Transition-metals photocatalysts for lignin valorization toward sustainable biofuel production[J]. Chinese Journal of Catalysis, 2026, 88: 35-85.

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Figures/Tables 30

Fig. 1. (a) Photocatalytic conversion of lignin into fuel pathways. (b) Statistical analysis of publications on photocatalytic conversion of lignin into fuels and precursors, 2014-2025.

Fig. 2. (a) Statistical distribution of transition metal catalysts for photocatalytic lignin conversion into fuels and precursors in the periodic table (through 2025). (b) Corresponding statistical chart.

Table 1 A comparison of the current study with other associated publications.

Ref.	Basic structural characteristics	Bond-breaking mechanism	Actual lignin conversion analysis	Transition metal materials	Gas and liquid fuel co-production	Fuel precursor upgrade	Economic and environmental impact evaluation
[12]	✔	✔					
[13]	✔		✔				
[14]	✔					✔	
[15]	✔		✔			✔	
[16]					✔		
[17]	✔						✔
[18]	✔	✔					
[19]		✔	✔				
This work	✔	✔	✔	✔	✔	✔	✔

Fig. 3. (a) Typical structural models of lignin. (b) Major monomeric units. (c) Characteristic linkage bonds in lignin. (d) Pretreatment methods for lignin.

Table 2 Comparative analysis of lignin traits from diverse isolation techniques [31,55].

Lignin category	Extraction conditions	Molecular formula	Molecular weight (g/mol)	Polydispersity (PDI)	Solubility
Kraft lignin	H₂O, NaOH, Na₂S, 150-180 °C	C₉H_8.5O_2.1S_0.1(OCH₃)_0.8(CO₂H)_0.2	180	2-4	alkali, strongly polar organic solvents
Lignosulfonate (Softwood)	H₂O, sulfites, 120-180 °C	C₉H_8.5O_2.5(OCH₃)_0.85(SO₃H)_0.4	215−254	4-9	water
Lignosulfonate (Hardwood)	H₂O, sulfites, 120-180 °C	C₉H_7.5O_2.5(OCH₃)_0.39(SO₃H)_0.6	188	4-9	water
Organosolv lignin	High-boiling-point solvents, organic acids, etc., 180-210 °C	C₉H_8.53O_2.45(OCH₃)_1.04	~188	2.4-6.4	alkali, polar organic solvents
Steam explosion lignin	H₂O, high temperature, and pressure	C₉H_8.53O_2.45(OCH₃)_1.04	~188	1.5-2.8	higher than Kraft lignin in organic solvents

Fig. 5. (a) Energy-level diagram illustrating the conversion of reactants (R) to products (P) via thermal and photocatalytic processes. Here, C, E, and S denote the catalyst, ambient molecules (solvent and atmosphere), and byproducts, respectively. Adapted with permission [77]. Copyright 2020, Royal Society of Chemistry. (b) Representative semiconductor band edge positions based on redox potential. (c) Diagram depicting the mechanism by which lignin is photocatalytically converted into gas and liquid fuels.

Scheme 1. Depolymerization of β-O-4 model C-O bonds through a two-step approach (a) and a one-step approach. Adapted with permission [88]. Copyright 2014, American Chemical Society. Adapted with permission [89]. Copyright 2016, American Chemical Society. (b) The cleavage of C-O bonds mainly involves two methods: two-step depolymerization and one-step depolymerization.: two-step depolymerization and one-step depolymerization. Adapted with permission [90]. Copyright 2020, American Chemical Society. Adapted with permission [91]. Copyright 2024, Elsevier.

Fig. 6. (a) Mechanism of ZT-70 n-n heterojunction depolymerization of the β-O-4 model. Adapted with permission [93]. Copyright 2025, American Chemical Society. (b) Schematic diagram of photocatalytic breakdown pathway of lignin using 10% CN/5CQD/CZS. Adapted with permission [94]. Copyright 2024, Royal Society of Chemistry.

Table 3 Photocatalytic transformation of β-O-4 lignin models targeting C-O bond cleavage.

β-O-4 model compound	Reaction type		Photocatalyst		Conversion (%)		Main products		Ref.
	—		H-TiO₂		100		phenol, styrene		[98]
	—		Ti-N-NPs		100		phenol (49%), styrene (51%)		[95]
	two-step reaction		Pd/ZnIn₂S₄, TiO₂		99		phenol (93%), acetophenone (90%)		[89]
			g-C₃N₄/Zn₄In₂S₇		99		phenol (93.4%), acetophenone (75.2%)		[99]
			CdS-SH/TiO₂		99		phenol (85%), acetophenone (87%)		[100]
			MoS₂/ZnIn₂S₄		100		phenol (86.6%), acetophenone (82.3%)		[101]
			g-C₃N₄/CQD/ZnS		84		phenol (60%), acetophenone (60.2%)		[94]
			Au-H-TiO₂		—		phenol, acetophenone (60.2%)		[102]
			(100) CdS@(220) CdS		100		phenol (94.3%), acetophenone (93.4%)		[103]
			CdSe@CdS		94		phenol (67%), acetophenone (66%)		[104]
	one-step reaction		Cr/ZnIn₂S₄		~100		phenol (96%), acetophenone (95%)		[105]
			FeCoRu@SiO₂-TiO₂		> 90		phenol (55.6%), acetophenone (32.8%)		[106]
			g-C₃N₄/ZnIn₂S₄		99		phenol, acetophenone		[107]
			CdS/UiO-66		90		phenol, acetophenone		[108]
			Ce₂S₃/TiO₂		94.6		phenol (94%), acetophenone (80%)		[109]
			SiO₂-TiO₂		—		phenol, acetophenone		[110]
			ZIS		~100		phenol (91.2%), acetophenone (91.7%)		[97]
			Ag₂S@CdS		99		phenol (95%), acetophenone (91%)		[90]
	one-step reaction		Bi₂O₃/Bi₂WO₆		85.62		phenol, guaiacol, p-hydroxybenzaldehyde		[91]
	two-step reaction		CdSe QDs		90		4'-methoxyacetophenone, guaiacol		[111]
	—		PDI		86		phenols, ketones		[112]
	two-step reaction		NiO/TiO₂		99		phenol (96%), acetophenone (78%)		[113]
	two-step reaction		TiO₂		100		acetophenone (88%), guaiacol (73%)		[114]
	two-step reaction		ZnIn₂S₄/TiO₂		98		phenol (85%), acetophenone (67%)		[93]
	two-step reaction		CzCPs		—		phenol (86%), acetophenone		[115]
		two-step reaction		CuBr₂, Zn		> 99		phenol (98%), acetophenone (99%)		[116]
		two-step reaction		Zn₄In₂S₇/g-C₃N₄		99		phenol (87%), acetophenone (86%)		[117]
		two-step reaction		Ir(ppy)₂(bpy)-MCFs		> 90		4'-methoxyacetophenone (98%), guaiacol (97%)		[118]
,		one-step reaction		ZmIn₂S_m₊₃, m = 1‒6		99		phenol (86%), acetophenone (82%)		[119]
		two-step reaction		[4-AcNH-TEMPO]BF₄ (bobbitt salt), [Ir(ppy)₂(dtbbpy)]PF₆		—		4'-Methoxyacetophenone (88%), guaiacol (89%)		[88]
,		—		Cu (bathocup)(XantPhos) BF₄		—		acetophenone (70%)		[120]

Table 3 Photocatalytic transformation of β-O-4 lignin models targeting C-O bond cleavage.

β-O-4 model compound	Reaction type		Photocatalyst		Conversion (%)		Main products		Ref.
	—		H-TiO₂		100		phenol, styrene		[98]
	—		Ti-N-NPs		100		phenol (49%), styrene (51%)		[95]
	two-step reaction		Pd/ZnIn₂S₄, TiO₂		99		phenol (93%), acetophenone (90%)		[89]
			g-C₃N₄/Zn₄In₂S₇		99		phenol (93.4%), acetophenone (75.2%)		[99]
			CdS-SH/TiO₂		99		phenol (85%), acetophenone (87%)		[100]
			MoS₂/ZnIn₂S₄		100		phenol (86.6%), acetophenone (82.3%)		[101]
			g-C₃N₄/CQD/ZnS		84		phenol (60%), acetophenone (60.2%)		[94]
			Au-H-TiO₂		—		phenol, acetophenone (60.2%)		[102]
			(100) CdS@(220) CdS		100		phenol (94.3%), acetophenone (93.4%)		[103]
			CdSe@CdS		94		phenol (67%), acetophenone (66%)		[104]
	one-step reaction		Cr/ZnIn₂S₄		~100		phenol (96%), acetophenone (95%)		[105]
			FeCoRu@SiO₂-TiO₂		> 90		phenol (55.6%), acetophenone (32.8%)		[106]
			g-C₃N₄/ZnIn₂S₄		99		phenol, acetophenone		[107]
			CdS/UiO-66		90		phenol, acetophenone		[108]
			Ce₂S₃/TiO₂		94.6		phenol (94%), acetophenone (80%)		[109]
			SiO₂-TiO₂		—		phenol, acetophenone		[110]
			ZIS		~100		phenol (91.2%), acetophenone (91.7%)		[97]
			Ag₂S@CdS		99		phenol (95%), acetophenone (91%)		[90]
	one-step reaction		Bi₂O₃/Bi₂WO₆		85.62		phenol, guaiacol, p-hydroxybenzaldehyde		[91]
	two-step reaction		CdSe QDs		90		4'-methoxyacetophenone, guaiacol		[111]
	—		PDI		86		phenols, ketones		[112]
	two-step reaction		NiO/TiO₂		99		phenol (96%), acetophenone (78%)		[113]
	two-step reaction		TiO₂		100		acetophenone (88%), guaiacol (73%)		[114]
	two-step reaction		ZnIn₂S₄/TiO₂		98		phenol (85%), acetophenone (67%)		[93]
	two-step reaction		CzCPs		—		phenol (86%), acetophenone		[115]
		two-step reaction		CuBr₂, Zn		> 99		phenol (98%), acetophenone (99%)		[116]
		two-step reaction		Zn₄In₂S₇/g-C₃N₄		99		phenol (87%), acetophenone (86%)		[117]
		two-step reaction		Ir(ppy)₂(bpy)-MCFs		> 90		4'-methoxyacetophenone (98%), guaiacol (97%)		[118]
,		one-step reaction		ZmIn₂S_m₊₃, m = 1‒6		99		phenol (86%), acetophenone (82%)		[119]
		two-step reaction		[4-AcNH-TEMPO]BF₄ (bobbitt salt), [Ir(ppy)₂(dtbbpy)]PF₆		—		4'-Methoxyacetophenone (88%), guaiacol (89%)		[88]
,		—		Cu (bathocup)(XantPhos) BF₄		—		acetophenone (70%)		[120]

Fig. 7. (a) Graphical illustration of the preparation of Ce2S3/TiO2 S-scheme heterojunctions. (b) Schematic diagram of process improvement for Ce2S3/TiO2 S-scheme heterojunction photocatalytic depolymerization of PP-ol. (c) Work function of Ce2S3/TiO2. (d) Schematic diagram of the mechanism of photocatalytic lignin cracking on Ce2S3/TiO2. Reproduced with permission [109]. Copyright 2024, American Chemical Society. Schematic illustration of the preparation (e) and charge density distribution (f) of a half-unit-cell MoS2/ZnIn2S4 monolayer. (g) DFT calculations of BDE for EPP-ol and Cα-H bonds and DF for LCα-H under different conditions. (h) Conversion efficiency and product yield of PP-ol photocatalytic conversion by MoS2/ZIS-300 at different concentrations. (i) Effect of water volume on PP-ol conversion rate and product yield. Reproduced with permission [101]. Copyright 2024, American Chemical Society.

Scheme 2. Primary reaction (a) and minor reaction (b) of C-C bond depolymerization in the β-O-4 model. (c) Proposed mechanism for C-C bond depolymerization in the β-O-4 model.

Table 4 Photocatalytic C-C bond cleavage in β-O-4 lignin model compounds.

β-O-4 model compound	Light source		Photocatalyst		Conversion (%)	Main products		Ref.
	visible light		C₃N₄		94	benzaldehyde (60%), benzoic acid (16%)		[137]
	simulated sunlight		CuO/BiVO₄		86.5	aromatic compounds (665.03 μmol g_cat⁻¹ h⁻¹)		[138]
	UV		P₂W₁₇V (001)/-TiO₂		98.8	benzaldehyde (72%)		[135]
	visible light		urchin-like Nb₂O₅ hollow microspheres		94	benzaldehyde, phenyl formate, benzoic acid		[134]
	blue LED		triazine-heptazine-based carbon nitride		96.1	benzaldehyde (60.3%), phenyl formate (47.9%)		[139]
	simulated sunlight		g-C₃N₄/rGO/CdS		95	benzaldehyde (71%), phenyl formate (69%)		[140]
	visible light		Ru₁/MCN		93	benzaldehyde (92%), phenyl formate (90%),		[141]
	simulated sunlight		p-CN/p-PDI		99	benzaldehyde (59%), phenyl formate (37%), benzoic acid (7%)		[142]
		simulated sunlight		Keplerate polyoxometalates	97.8		phenyl formate (8.8%), benzaldehyde (0.2%)	[143]
		visible light		Fe/mpg-CN	98		benzaldehyde (82%), phenyl formate (36%), benzoic acid (15%)	[144]
		simulated sunlight		H₅PMo₁₀V₂O₄₀/ g-C₃N₄(HPA/CN)	97.4		benzaldehyde (62.7%), benzoic acid (42.5%), phenyl formate (16.0%)	[145]
		visible light		Zn/CN	99		benzoic acid, benzaldehyde, benzoic acid methyl ester, and ketones	[146]
		visible light		g-C₃N₄/CQDs/WO₃	99		benzoic acid, benzaldehyde (83.92%)	[147]
		visible light		g-C₃N₄ (PTCN)	97.2		benzoic acid (22.0%), benzaldehyde (13.0%), and phenyl formate (2.1%)	[148]
		visible light		Bi/CTF	78.4		benzoic acid (65.2%), benzaldehyde (81.4%), and phenyl formate (52.6%)	[149]
,		simulated sunlight		Cu₂S/g-C₃N₄	93.2		aromatic compounds (1346.71 μmol g_cat⁻¹ h⁻¹)	[150]
		visible light		M-TiO₂/g-C₃N₄	96.8		benzaldehyde (86.4%)	[75]
		simulated sunlight		RuC/TiO₂ NPs	—		3,4-dimethoxybenzaldehyde (52%), 2-(2-methoxyphenoxy)- acetaldehyde (36%)	[151]
,		visible light		CdS/2D g-C₃N₄	—		best CRAM (96.5%)	[76]
		visible light		R-C_3‒_xN₄	89		benzaldehyde (85%)	[152]

Table 4 Photocatalytic C-C bond cleavage in β-O-4 lignin model compounds.

β-O-4 model compound	Light source		Photocatalyst		Conversion (%)	Main products		Ref.
	visible light		C₃N₄		94	benzaldehyde (60%), benzoic acid (16%)		[137]
	simulated sunlight		CuO/BiVO₄		86.5	aromatic compounds (665.03 μmol g_cat⁻¹ h⁻¹)		[138]
	UV		P₂W₁₇V (001)/-TiO₂		98.8	benzaldehyde (72%)		[135]
	visible light		urchin-like Nb₂O₅ hollow microspheres		94	benzaldehyde, phenyl formate, benzoic acid		[134]
	blue LED		triazine-heptazine-based carbon nitride		96.1	benzaldehyde (60.3%), phenyl formate (47.9%)		[139]
	simulated sunlight		g-C₃N₄/rGO/CdS		95	benzaldehyde (71%), phenyl formate (69%)		[140]
	visible light		Ru₁/MCN		93	benzaldehyde (92%), phenyl formate (90%),		[141]
	simulated sunlight		p-CN/p-PDI		99	benzaldehyde (59%), phenyl formate (37%), benzoic acid (7%)		[142]
		simulated sunlight		Keplerate polyoxometalates	97.8		phenyl formate (8.8%), benzaldehyde (0.2%)	[143]
		visible light		Fe/mpg-CN	98		benzaldehyde (82%), phenyl formate (36%), benzoic acid (15%)	[144]
		simulated sunlight		H₅PMo₁₀V₂O₄₀/ g-C₃N₄(HPA/CN)	97.4		benzaldehyde (62.7%), benzoic acid (42.5%), phenyl formate (16.0%)	[145]
		visible light		Zn/CN	99		benzoic acid, benzaldehyde, benzoic acid methyl ester, and ketones	[146]
		visible light		g-C₃N₄/CQDs/WO₃	99		benzoic acid, benzaldehyde (83.92%)	[147]
		visible light		g-C₃N₄ (PTCN)	97.2		benzoic acid (22.0%), benzaldehyde (13.0%), and phenyl formate (2.1%)	[148]
		visible light		Bi/CTF	78.4		benzoic acid (65.2%), benzaldehyde (81.4%), and phenyl formate (52.6%)	[149]
,		simulated sunlight		Cu₂S/g-C₃N₄	93.2		aromatic compounds (1346.71 μmol g_cat⁻¹ h⁻¹)	[150]
		visible light		M-TiO₂/g-C₃N₄	96.8		benzaldehyde (86.4%)	[75]
		simulated sunlight		RuC/TiO₂ NPs	—		3,4-dimethoxybenzaldehyde (52%), 2-(2-methoxyphenoxy)- acetaldehyde (36%)	[151]
,		visible light		CdS/2D g-C₃N₄	—		best CRAM (96.5%)	[76]
		visible light		R-C_3‒_xN₄	89		benzaldehyde (85%)	[152]

Fig. 8. Charge transport pathways in S-scheme (a), type-II (b), and Z-scheme (c) heterojunction systems.

Fig. 9. (a) Synthesis pathways for POSS-PDI, p-CN, and their composite p-CN/P-PDI, along with the proposed photocatalytic selective cleavage mechanism of the β-O-4 model compound within the p-CN/P-PDI S-scheme heterojunction. (b) Schematic diagram of the S-scheme heterojunction charge transfer process. (c) Fluorescence lifetime decay profiles of POSS-PDI, p-CN, and the composite p-CN/P-PDI-3. (d) Electron density difference between p-CN and CPDI (isosurface value: 103 e Å?3), with yellow and cyan areas representing charge accumulation and depletion. Reproduced with permission [142]. Copyright 2023, Wiley-VCH GmbH. (e) PP-ol conversion efficiency and product distribution over different catalytic materials. (f) N2 adsorption-desorption isotherms of M-TiO2, g-C3N4, MTCN-10, and O-TiO2. (g) UV-vis reflectance spectra of M-TiO2, g-C3N4, and MTCN-10. (h) EPR spectra of oxygen adducts formed on TEMP-1 and MTCN-10 under dark conditions and after 10 min of illumination. (i) Mechanism of Cα-Cβ bond photolysis of PP-ol catalyzed by MTCN-10. Reproduced with permission [75]. Copyright 2025, Elsevier.

Fig. 10. (a) Proposed mechanism for visible-light-induced C-C bond cleavage in PP-ol. Reproduced with permission [165]. Copyright 2023, American Chemical Society. (b) Postulated pathway for the photocatalytic scission of the Cα-Cβ bond in pp-ol using CB-3. Reproduced with permission [149]. Copyright 2025, Elsevier. (c) Proposed mechanisms for the photocatalytic depolymerization of model compounds by AgI/BSO-5. Reproduced with permission [166]. Copyright 2025, Elsevier. (d) Proposed reaction mechanism for the cleavage of PP-ol on two-dimensional g-C3N4 and Cu/2D g-C3N4 surfaces. Reproduced with permission [167]. Copyright 2025, Elsevier.

Scheme 3. (a) Schematic diagram of 4-O-5 model depolymerization. Adapted with permission [170]. Copyright 2020, Springer Nature. (b) Schematic illustration of α-O-4 model depolymerization. Adapted with permission [171]. Copyright 2024, Royal Society of Chemistry. (c) Schematic illustration of β-1 model depolymerization. Adapted with permission [172]. Copyright 2019, American Chemical Society.

Table 5 Summary of model compound types and their cleavage mechanisms.

Model type	Representative structure	Primary bond cleavage	Key active species	Typical products	Ref.
β-O-4	PP-ol, MP-ol	C-O (C_β-O)/C-C (C_α-C_β)	h⁺, •O₂^‒, ¹O₂	phenol, acetophenone, benzaldehyde, benzoic acid	[70,90,178]
α-O-4	benzyl phenyl ether	C-O (C_α-O)	h⁺, •OH	benzaldehyde, phenol	[179]
4-O-5	Diaryl ether	C-O	carboxyl radical	aromatic carboxylic acids, phenols	[171]
β-1	1,2-diphenylethanol	C-C (C_α-C_β)	LMCT, alkoxy radical	benzaldehyde, benzoic acid	[175,180,181]
β-5/5-5'	biphenyl-type structure	C-C	•O₂^‒	aromatic aldehydes/acids	[18, 182]

Fig. 11. Summary of different catalysts used for the photocatalytic transformation of model lignin compounds into fuel precursors.

Fig. 12. (a) Diagram illustrating the synthesis of CdS/BiOI with iodine vacancies. (b) SEM micrographs and EDS patterns of C/B-0.75-400. Photocurrent responses (c) and EIS Nyquist spectra (d) for CdS, BiOI, BiOI-VI, C/B-0.75, and C/B-0.75-400. (e) Vanillin yield at different calcination temperatures. (f) Proposed mechanism for SLS photocatalytic production of vanillin on CdS/BiOI with or without iodine vacancies. Reproduced with permission [197]. Copyright 2023, Elsevier. (g) Illustrated schematic of M-TiO2 preparation. (h) XPS spectra of MT400 and MIL-125: O 1s survey scan. Aperture distribution diagrams (i) and corresponding hv curves (j) for MIL-125, MT400, MT500, and MT600. (k) XRD patterns and SEM micrographs of MT400 before and after photocatalytic conversion of SLS. (l) Trapping experiments for vanillin production utilizing MT400. (m) Proposed mechanism of SLS photocatalytic conversion over MT400. Reproduced with permission [198]. Copyright 2021, Elsevier.

Fig. 13. Summary of the actual lignin characteristics of the representative samples and the properties of the catalysts employed in the depolymerization process.

Fig. 14. (a) Schematic diagram of photoreforming lignocellulose to produce H2 using NCNCNx and H2 production co-catalysts. Reproduced with permission [225]. Copyright 2018, American Chemical Society. (b) TAH of lignocellulose. Reproduced with permission [227]. Copyright 2022, Elsevier. (c) Schematic diagram of the indirect oxidation process for the photocatalytic conversion of lignocellulose to H2 using PtSA-CdS. Reproduced with permission [228]. Copyright 2024, Wiley-VCH GmbH. (d) Illustrative diagram depicting synergistic H2 production via photocatalytic biomass conversion on CNx/Co. Reproduced with permission [229]. Copyright 2025, American Chemical Society.

Fig. 15. (a) Schematic preparation of Mo2C catalyst. (b) Glucose molecules adsorbed on the Mo2C surface exhibit a double-vacancy equilibrium structure. Reproduced with permission [239]. Copyright 2024, Wiley-VCH GmbH. (c) Electron density difference of Pt/TiO2-OV(M). (d) 4-MBA oxidation. (e) Electron density difference of Pt/TiO2-OV(M). Reproduced with permission [242]. Copyright 2024. American Chemical Society. Elemental mapping images of Pt-decorated InGaN NWs (f) and FeMn-modified InGaN nanowires (g). (h) Time-resolved PL spectra of InGaN nanowires and Pt/InGaN NWs. (i) Photocatalytic synthesis gas activity of various lignin-derived model compounds. Reproduced with permission [247]. Copyright 2024, Wiley-VCH GmbH. (j) Schematic diagram of the proposed mechanism for generating syngas from lignin at the FeMn/InGaN interface. (k) Quasi-in-situ EPR characterization of lignin reforming over FeMn/InGaN catalysts (l) Stepwise energy of H atom desorption from adsorbed CH3 radical. (m) CO adsorption on Fe4/GaN, Fe3Mn1/GaN, Fe2Mn2/GaN, and Fe1Mn3/GaN models. Green, light blue, purple, bronze, brown, red, and light pink represent Ga, N, Mn, Fe, C, O, and H, respectively. Reproduced with permission [248]. Copyright, 2024, Wiley-VCH GmbH.

Fig. 16. Advantages and challenges of producing gaseous fuels from lignin, and catalyst design strategies.

Fig. 17. Process diagram illustrating the photocatalytic transformation of lignin into fuels.

Fig. 18. (a) Proposed mechanism of Suzuki catalytic coupling under UV irradiation. Reproduced with permission [280]. Copyright 2023, Elsevier. (b) Proposed mechanism for the conversion of benzaldehyde to hydroxybenzaldehyde and benzyl alcohol. Reproduced with permission [276]. Copyright 2020, American Chemical Society. (c) Mechanistic proposal for light-driven C-C coupling of benzyl alcohol. Reproduced with permission [277]. Copyright 2024, Royal Society of Chemistry. (d) Proposed mechanism for photocatalytic C-C coupling of phenylmethanol on Sulfur-doped CdS Nanospheres. Reproduced with permission [282]. Copyright 2025, American Chemical Society. (e) Proposed reaction mechanism of TEMPO (HT-1) (0.05 mmol) with 1a (0.1 mmol) in DMF (2.5 mL). Reproduced with permission [283]. Copyright 2024, Springer Nature. (f) Concentration distribution curves of reactants and products during the cyclization reaction of ethyl benzoate on Cu/C and Pd/C surfaces. Reproduced with permission [284]. Copyright 2024, American Chemical Society.

Fig. 19. Analysis chart of the potential of lignin downstream products as fuel precursors.

Fig. 20. (a) Assessment of ecological effects in lignin photodegradation using different catalytic conditions. (b) Relative percentage contribution of each sub-process to the production of 1 kg of vanillin during catalytic lignin photodegradation. (c) Environmental footprint analysis of SRQHR-activated versus conventional catalyst synthesis routes. (d) Environmental impact evaluation of catalyst reuse during lignin photodegradation. Reproduced with permission [289]. Copyright 2020, Elsevier.

Fig. 21. Summary of transition metal catalysts for the photocatalytic upgrading of lignin to liquid fuel precursors and gaseous fuels.

Fig. 22. Schematic diagram summarizing and outlining the prospects for photocatalytic lignin upgrading to fuels and precursors.

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Transition-metals photocatalysts for lignin valorization toward sustainable biofuel production

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