Cβ Bond Research Articles

Efficient cleavage of Cα[sbnd]Cβ bonds in lignin using tetrabutylammonium tetrafluoroborate as both the catalyst and auxiliary electrolyte

Lignin is a promising alternative to fossil resources due to its abundance of benzene ring monomers. However, the stability of the CαCβ bond in lignin has hindered its efficient depolymerization. Electrochemical methods for breaking this bond are not well-studied. This paper presents a novel approach for catalytic depolymerization of lignin to produce acetals under mild conditions, without the need for additional catalysts. Under room temperature and in an air atmosphere, the combination of tetrabutylammonium tetrafluoroborate (TBABF4) as an auxiliary electrolyte and methanol (MeOH) as a solvent has shown high selectivity in catalyzing the cleavage of CαCβ bonds in lignin. Over 90.0 % of the resulting products are acetals, with the optimal conditions being a substrate concentration of 0.02 M, TBABF4 concentration of 0.008 M, a constant current of 30 mA, and a reaction time of 3 h. This led to a substrate conversion rate of 95.8 % and a product yield of 98.0 % for benzaldehyde dimethyl acetal (Bda). The mechanism study reveals that the tributyl ammonium radical cation decomposed by TBABF4 is adsorbed on the electrode surface. Subsequently, the adsorbed O2 is activated to form superoxide anion radical active species through single electron transfer, which plays a crucial catalytic role. TBABF4 acts as both an auxiliary electrolyte and a catalyst in this process. This research introduces a novel approach for electrocatalytic depolymerization of inert CαCβ bonds in lignin, leading to the selective conversion into acetal chemicals.

Efficient selective cleavage of C−C bonds in lignin under visible light enabled by the Fe-doped mesoporous graphitic carbon nitride photocatalyst

To obtain high-valued aromatic products, it is paramount to cleave the Cα−Cβ bonds in lignin under mild conditions selectively. Nevertheless, this task remains daunting due to the formidable dissociation energies and steric hindrance associated with these bonds. Herein, a facile, efficient and cost-effective strategy for selectively breaking the Cα−Cβ bond in lignin with visible-light irradiation and room temperature is proposed, facilitated by the utilization of the ferric-doped mesoporous graphitic carbon nitride (Fe/mpg-CN) photocatalyst. Collective contributed by the reduced band gap and photoluminescence, combined with intensified visible-light absorption and enhanced photocurrent, the effectiveness in photocatalytic activity of Fe/mpg-CN is offered. Specifically, a high conversion rate (98 %) of the lignin model compound (2-phenoxy-1-phenylethanol), coupled with an excellent selectivity of 98 % in cleaving the Cα−Cβ bonds is achieved by Fe/mpg-CN. Photogenerated holes are indicated as the main active species through comprehensive mechanistic investigations. Additionally, the successful photocatalytic depolymerization of the complex dimer model compound (conversion rate ∼ 96 %) and pine kraft lignin further corroborate the satisfying photocatalytic activity and selectivity of Fe/mpg-CN. This study introduces a promising and viable strategy for the selective breaking of lignin through photocatalysis, offering significant implications for the sustainable production of valuable aromatic compounds.

Reduction of the photogenerated electron transport path by modulating the conduction band region to achieve the highest lignin β–O–4 bond photocleavage efficiency under xenon excitation

Photocracking of lignin β–O–4 bonds is a green approach for the high-value modification of lignin. Graphitic carbon nitride (g-C3N4) that can photocleave the β–O–4 bond is presently the only stable, metal-free photocatalyst owing to the residual metal ions generated due to photocorrosion of metal sulfides. Herein, g-C3N4 with a N–C3 vacancy structure is prepared by etching site–engineering strategy based on the protection of C–N=C structure by chlorine atom. The N–C3 vacancy structure can reduce the transport path of the photogenerated electrons by tuning the conduction band (CB) region to the edge of the photocatalyst, which impedes the critical complexation of the photogenerated electron–hole pairs and enhances the photoelectric conversion efficiency five-fold. Combined with the unique chemisorption capacity (137.82 kJ/mol) of N–C3 vacancies for oxygen, the g-C3N4 photocatalysts with N–C3 vacancy structure can generate 9.6-fold higher superoxide radicals and 13-fold higher lignin β–O–4 bond photocleavage efficiency lignin compared with untreated g-C3N4. Based on the reaction enthalpy changes and free energies investigated through simulations, a route of lignin Cα–Cβ bonds being oxidized and dehydrogenated twice by photogenerated cavities is proposed for the first time. This work reveals the relation between the properties of g-C3N4 and the photocleavage efficiency of lignin β–O–4 bonds.

One‐Pot Catalytic Cascade for the Depolymerization of the Lignin β‐O‐4 Motif to Non‐phenolic Dealkylated Aromatics

Aromatic monomers obtained by selective depolymerization of the lignin β‐O‐4 motif are typically phenolic and contain (oxygenated) alkyl substitutions. This work reveals the potential of a one‐pot catalytic lignin β‐O‐4 depolymerization cascade strategy that yields a uniform set of methoxylated aromatics without alkyl side‐chains. This cascade consists of selective acceptorless dehydrogenation of the γ‐hydroxy group, subsequent retro‐aldol reaction cleaving the Cα–Cβ bond followed by in situ acceptorless decarbonylation of the formed aldehydes. This three‐step cascade reaction, catalyzed by an iridium(I)‐BINAP complex, resulted in 75% 1,2‐dimethoxybenzene from G‐type lignin dimers alongside syngas (CO:H2 ≈ 1.4:1). Applying this method to a synthetic G‐type polymer, 11 wt% 1,2‐dimethoxybenzene was obtained. This versatile compound can be easily transformed into 3,4‐dimethoxyphenol, a valuable precursor for pharmaceutical synthesis, through enzymatic catalytic approach. Moreover, the hydrodeoxygenation potential of 1,2‐dimethoxybenzene offers a pathway to produce valuable cyclohexane or benzene derivatives, presenting enticing opportunities for sustainable chemical transformations without the necessity for phenolic mixture upgrading via dealkylation.

Visible-light driven efficient cleavage of Cα–Cβ bond in lignin models and lignin over porous tubular carbon nitride

The photocatalytic selective breaking of recalcitrant Cα–Cβ bond in real lignin to product value-added chemicals under mild conditions is intriguing but remains challenging. Herein, a sustainable strategy for the efficient and selective breakage of Cα–Cβ bond in lignin β-O-4 model compounds and lignin over porous tubular g-C3N4 (PTCN) photocatalyst was designed under ambient conditions. Compared with bulk g-C3N4, the construction of PTCN not only facilitates photogenerated charge separation and transfer, but also provides more exposed interior active sites, which is conductive to reactant adsorption on the surface of PTCN, thereby resulting in the higher photocatalytic efficiency. With this strategy, 2-phenoxy-1-phenylethanol as the typical model substrate was completely converted into aromatic monomers with Cα–Cβ bond cleavage selectivity of 97.2 %. Both mechanistic studies and theoretical calculations revealed that the photogenerated holes, electrons and O2− respectively played an essential role in the Cβ–H dehydrogenation and Cα–Cβ bond breakage. Native lignin samples (alkaline, pine and wheat straw) were applied to these photocatalytic systems and successfully depolymerized with Cα–Cβ bond cleavage under optimal reaction conditions. This work could provide an in-depth insight into photocatalyst design for the economical and efficient valorization of lignin.

Efficient and selective cleavage of lignin C–C bonds under visible light facilitated by the Zn(II)-doped mesoporous graphitic carbon nitride photocatalyst

Despite the promise of photocatalysis for extracting aromatic compounds from renewable lignin feedstocks, the selective cleavage of Cα–Cβ bonds in lignin under mild conditions poses a persistent challenge, primarily due to their elevated dissociation energies and steric hindrance. Herein, an efficient photocatalytic strategy for selectively breaking the Cα–Cβ bonds of lignin with visible-light irradiation and room temperature is proposed, facilitated by the Zn(II)-doped porous graphitic carbon nitride (Zn/CN) photocatalyst. Reduced energy band gap and photoluminescence, along with intensified visible-light absorption and enhanced photocurrent of Zn/CN, contribute to its efficacy in photocatalytic activity. Consequently, the lignin model compound (2-phenoxy-1-phenylethanol) achieves a conversion rate of 99 %, demonstrating a notable selectivity of 97 % in specifically breaking the Cα–Cβ bonds. Mechanistic investigations identify that photogenerated holes play a pivotal role during the photocatalytic conversion. Additionally, the activity and selectivity of Zn/CN photocatalyst are further confirmed by the successful photocatalytic conversion of pine kraft lignin, yielding high-value chemicals such as benzoic acid and vanillin. This research proposes an economical, efficient, and facile method for utilizing renewable lignin feedstocks under photocatalysis, thus advancing the production of high-value aromatic compounds.

Theoretical Study on the Pyrolysis Mechanism of the Lignin Dimer Model Compound Catalyzed by Alkaline Earth Metal Ions Ca2+ and Mg2+

It is essential to investigate the influence of alkaline earth metals on the pyrolysis mechanism and resulting products of lignin to enhance the efficient thermochemical conversion and utilization of lignin or biomass. In this study, the density functional theory method was used to simulate the pyrolytic reaction pathways of a β-O-4 type lignin dimer model compound (1-methoxy-2-(4-methoxyphenethoxy)benzene, mc) affected by alkaline earth metal ions Ca2+ and Mg2+. The computational findings suggest that Ca2+ and Mg2+ tend to combine with the oxygen atom at the Cβ position and the oxygen atom on the methoxy group of the lignin dimer model compound, forming stable complexes that modify the bond lengths of the Cα–Cβ and Cβ–O bonds and affect their pyrolysis energy barriers. During the catalytic pyrolysis process, the presence of Ca2+ and Mg2+ can promote the concerted decomposition reaction, leading to increased production of products like 1-methoxy-4-vinylbenzene, 2-methoxyphenol and catechol. Meanwhile, they can suppress homolytic cleavage reactions of the Cβ–O and Cα–Cβ bonds, thereby hindering the formation of other products such as 1-ethyl-4-methoxybenzene and 2-hydroxybenzaldehyde.

The Triceptide Maturase OscB Catalyzes Uniform Cyclophane Topology and Accepts Diverse Gly-Rich Precursor Peptides.

Triceptides are a class of ribosomally synthesized and post-translationally modified peptides defined by an aromatic C(sp2) to Cβ(sp3) bond. The Gly-rich repeat family of triceptide maturases (TIGR04261) are paired with precursor peptides (TIGR04260) containing a Gly-rich core peptide. These maturases are prevalent in cyanobacteria and catalyze cyclophane formation on multiple Ω1-X2-X3 motifs (Ω1 = Trp and Phe) of the Gly-rich precursor peptide. The topology of the individual rings has not been completely elucidated, and the promiscuity of these enzymes is not known. In this study, we characterized all the cyclophane rings formed by the triceptide maturase OscB and show the ring topology is uniform with respect to the substitution at Trp-C7 and the atropisomerism (planar chirality). Additionally, the enzyme OscB demonstrated substrate promiscuity on Gly-rich precursors and can accommodate a diverse array of engineered sequences. These findings highlight the versatility and implications for using OscB as a biocatalyst for producing polycyclophane-containing peptides for biotechnological applications.

Exploring factors affecting the dissociation energies of C–O and C–C bonds in lignin oligomers

The bond dissociation energy (BDE) of lignin is a key factor for lignin depolymerization, assisting in revealing the depolymerization mechanism. However, the impact of substituent as well as solvent, which usually stay together, on BDE of lignin remains unclear. Here, density functional theory (DFT) calculation is employed to compute the BDE of C–O and C–C bonds in lignin oligomers with six substituents in four solvents. The relationship models between multiple factors and BDE are established using random forest algorithm, achieving a predictive accuracy of 0.97. The results show that oxidating hydroxyl to ketone benefits the cleavage of β-O-4 and β-1 bonds. Hydroxyl and methoxy effectively contribute to breaking the Cβ-1 and Cα–Cβ bonds in the β-1 dimer. Polar solvents combined with hydroxyl promote C–O bond dissociation, while alkyl-containing solvents favor C–C bond dissociation. These findings provide valuable insights into lignin depolymerization, pre-depolymerization structural modifications, and the prediction of depolymerization pathways.

Electroreduction mechanisms of meso-Tetraphenylphlorin cation in strongly acidic media of benzonitrile

In nonaqueous media free-base porphyrins are easily protonated by strong proton donors to form the diprotonated porphyrins. The two-electron reduction of these species leads to phlorin cation species. To investigate the electroreduction products that follow the formation of these species, we evaluate the effect of increasing amounts of HClO4 on the electroreduction mechanism of the phlorin cation of meso-tetraphenyl porphyrin. We demonstrate that the phlorin cation undergoes a reversible protonation reaction to form a porphodimethene, which is further reduced to yield the chlorin-phlorin cation, a 4-electron reduced phlorin macrocycle with a hydrogenated pyrrolic Cβ = Cβ double bond. This undergoes further protonation and a 2-electron reduction to form a phlorin macrocycle, the bacteriochlorin-phlorin cation, wherein two pyrrole rings are hydrogenated. All these reduction processes occur at similar potential values, yet we managed to selectively form the 2-, 4- or 6- electron reduced product by a strict control of the number of protons in the medium. To the best of our knowledge, this is the first report of the electrochemical reduction of Cβ = Cβ bonds of pyrrolic rings. Thus, a new pathway for the electrochemical reduction of porphyrins is proposed.

Exploring helix structures of γ-peptides based on 2-(aminomethyl)cyclopentanecarboxylic acid.

Conformational search and density functional theory calculations were performed to explore the preferences of helical structures for chiro-specific oligo-γ-peptides of 2-(aminomethyl)cyclopentanecarboxylic acid (γAmc5) with a cyclopentyl constraint on the Cα-Cβ bond in solution. The dimer and tetramer of γAmc5 (1) with homochiral (1S, 2S) configurations exhibited a strong preference for the 9-membered helix foldamer in solution, except for the tetramer in water. However, the oligomers of γAmc5 (1) longer than tetramer preferentially adopted a right-handed (P)-2.614-helix (H1-14) as the peptide sequence becomes longer and as solvent polarity increases. The high stabilities for H1-14 foldamers of γAmc5 (1) in solution were ascribed to the favored solvation free energies. The calculated mean backbone torsion angles for H1-14 helix foldamers of γAmc5 (1) were similar to those calculated for oligomers of other γ-residues with cyclopentane or cyclohexane rings. However, the substitution of cyclopentane constraints on the Cα-Cβ bond of the γAmc5 (1) residue resulted in different conformational preferences and/or handedness of helix foldamers. In particular, the pyrrolidine-substituted analogs of the H1-14 foldamers of γAmc5 (1) with adjacent amine diads substituted at a proximal distance are expected to be potential catalysts for the crossed aldol condensation in nonpolar and polar solvents.

Tungstoborate heteropolyacid-catalyzed lignin liquefaction: Product yield and component distribution

Tungstoborate heteropolyacid catalysts have good catalytic degradation performance, especially for selective cleavage of C–C bonds in biomass. In this paper, the product yield and component distribution of tungstoborate heteropolyacid (BW12)-catalyzed lignin liquefaction were investigated at different parameters, including temperatures (120, 140, 160, 180, and 200 °C), catalyst amount (0, 2.5, 5, 10, and 20 wt. %), and reaction time (0, 30, 60, 90, and 120 min). It was found that a higher conversion (72.16 wt. %) and bio-oil yield (68.41 wt. %) could be obtained under suitable reaction conditions (180 °C, 60 min, 5 wt. %). Bio-oil analysis showed that the BW12 catalyst had a significant effect on the distribution of bio-oil fractions, in which mono-aromatic components increased from 32.96% to 47.56% compared to those without the catalyst. In particular, carbonyl substances in the mono-aromatic components increased from 18.66% to 26.97%. Spectroscopic analysis (FT-IR) found that the absorption peaks of C–O and C–C bonds in the liquefied residue catalyzed by BW12 decreased compared to the raw lignin. Moreover, the mechanism of BW12-catalyzed lignin depolymerization was investigated by DFT simulations. The simulation results demonstrated that the shortening of Cα–O bond, the breaking of Cβ–Cγ and Cα–Cβ bonds in lignin promoted the formation of vanillin and benzaldehyde, 3-hydroxy-4-methoxy. Finally, based on the experimental data and simulation results, a possible reaction pathway for the BW12-catalyzed liquefaction of lignin into mono-aromatic substances was proposed.

S-scheme Cs3Bi2Br9/Bi2WO6 heterojunctions for efficient photocatalytic cleavage of C–C bonds in β-1 lignin models

The efficient visible-light-driven cleavage of Cα–Cβ bonds was realized through green and sustainable methods using a lead-free S-scheme perovskite heterojunction.

Photoinduced organocatalytic lignin C–C bond cleavage in mixed binary solvents

Lignin presents a renewable alternative of fossil feedstock to produce value-added aromatic chemicals. Oxidative cleavage of C−C bonds in lignin is of great importance, but obtaining aromatic monomers in high selectivity under mild conditions is challenging. Herein, we report a novel strategy of photoinduced oxidative C–C cleavage of lignin β–O–4 derivatives using photoredox organocatalysts, among which Mes-10-phenyl-Acr+-BF4– exhibited high yields of aromatic aldehydes and phenyl formate. Besides, mixed binary organic solvents were demonstrated to promote bond cleavage and inhibit over-oxidation side reactions. The absorbance, excitation, and interaction with the lignin model of the photocatalyst in different solvents were investigated by UV-Vis, PL, and CV tests. Furthermore, through mechanism studies, a C-centered radical intermediate was captured, providing evidence for the direct Cα−Cβ bond cleavage mechanism during the reaction. This work presents a new photocatalytic strategy and provides deep insights into the bond cleavage mechanism for lignin valorization.

Differentiation of free d-amino acids and amino acid isomers in solution using tandem mass spectrometry of hydrogen-bonded clusters

Free d-amino acids and amino acid isomers were differentiated using tandem mass spectrometry without chromatographic separation. Ultraviolet photodissociation and water adsorption of leucine (Leu) and isoleucine (Ile) enantiomers hydrogen-bonded with tryptophan (Trp) were investigated at 8 K in the gas phase. The enantiomer-selective Cα–Cβ bond cleavage of Trp was observed in the product ion spectra obtained by 285 nm photoexcitation, where the abundance of NH2CHCOOH-eliminated ion of heterochiral H+(d-Trp)(l-Leu) was higher than that of homochiral H+(l-Trp)(l-Leu). When comparing water adsorption on the surfaces of the heterochiral and homochiral clusters in a cold ion trap, the number of water molecules adsorbed on the heterochiral cluster was greater than that adsorbed on the homochiral cluster. These results indicate that the stronger intermolecular interactions within the homochiral H+(l-Trp)(l-Leu) compared to the heterochiral cluster inhibit enantiomer-selective photodissociation. Leu and Ile were differentiated by the isomer-selective Cα–Cβ bond cleavage of Trp in the clusters. Calibration curves for the differentiation of isomeric amino acids and their enantiomers were developed using monitoring isomer- and enantiomer-selective photodissociation, indicating that the molar fractions in solution could be determined from a single product ion spectrum.

Radical-Mediated Photocatalysis for Lignocellulosic Biomass Conversion into Value-Added Chemicals and Hydrogen: Facts, Opportunities and Challenges.

Photocatalytic biomass conversion into high-value chemicals and fuels is considered one of the hottest ongoing research and industrial topics toward sustainable development. In short, this process can cleave Cβ -O/Cα -Cβ bonds in lignin to aromatic platform chemicals, and further conversion of the polysaccharides to other platform chemicals and H2 . From the chemistry point of view, the optimization of the unique cooperative interplay of radical oxidation species (which are activated via molecular oxygen species, ROSs) and substrate-derived radical intermediates by appropriate control of their type and/or yield is key to the selective production of desired products. Technically, several challenges have been raised that face successful real-world applications. This review aims to discuss the recently reported mechanistic pathways toward selective biomass conversion through the optimization of ROSs behavior and materials/system design. On top of that, through a SWOT analysis, we critically discussed this technology from both chemistry and technological viewpoints to help the scientists and engineers bridge the gap between lab-scale and large-scale production.

Radical‐Mediated Photocatalysis for Lignocellulosic Biomass Conversion into Value‐Added Chemicals and Hydrogen: Facts, Opportunities and Challenges

AbstractPhotocatalytic biomass conversion into high‐value chemicals and fuels is considered one of the hottest ongoing research and industrial topics toward sustainable development. In short, this process can cleave Cβ−O/Cα−Cβ bonds in lignin to aromatic platform chemicals, and further conversion of the polysaccharides to other platform chemicals and H2. From the chemistry point of view, the optimization of the unique cooperative interplay of radical oxidation species (which are activated via molecular oxygen species, ROSs) and substrate‐derived radical intermediates by appropriate control of their type and/or yield is key to the selective production of desired products. Technically, several challenges have been raised that face successful real‐world applications. This review aims to discuss the recently reported mechanistic pathways toward selective biomass conversion through the optimization of ROSs behavior and materials/system design. On top of that, through a SWOT analysis, we critically discussed this technology from both chemistry and technological viewpoints to help the scientists and engineers bridge the gap between lab‐scale and large‐scale production.

Hexaniobate as a Recyclable Solid Base Catalyst to Activate C–H Bonds in Lignin Linkage Boosting the Production of Aromatic Monomers

The targeting cleavage of lignin into value-added aromatic monomers has attracted increasing attention. Although the base-catalyzed depolymerization of lignin has been developed, the use of excess corrosive bases and their poor recyclability limit their industrial implementation. Herein, a catalytic amount of solid base K7HNb6O19 (KNb6) coupled with copper-modified graphitic carbon nitride (Cu/C3N4) shows enhanced catalytic performance for the oxidative cleavage of β-O-4 lignin linkages using molecular oxygen. Due to the synergetic effect between KNb6 and Cu/C3N4, 96% of the β-O-4 ketone model was converted under relatively mild conditions, and phenol (yield: 90%) and other aromatic monomers (yield: 90%) were obtained. Moreover, KNb6–Cu/C3N4 is robust, and its catalytic activity is basically maintained after five cycles. Experimental and theoretical studies (spectroscopic analysis, control experiments, kinetic study, density functional theory calculations, etc.) reveal that the surface basic O atoms of KNb6 can simultaneously activate the Cβ–H bond of β-O-4 ketone to promote the insertion of molecular oxygen, and subsequently, Cu/C3N4 catalyzes the selective cleavage of the Cα–Cβ bond. The catalysts were also active for the oxidative cleavages of other lignin models and oxidized organosolv lignin.

Electrocatalysis Cα–Cβ and Cβ–O bond cleavage of lignin model compound using Ni-Co/C as catalyst electrode in deep eutectic solventx

In this study, Cα–Cβ and Cβ–O bond cleavage of β-O-4 model compound (2-phenoxy-1-phenylethanol) were accomplished by electrocatalysis depolymerization process in deep eutectic solvents (DES) systems. We have investigated the application of Ni-Co/C catalysts on working electrode, which were synthesized with impregnation method. The Ni-Co/C with porous structure and abundant active sites, was shown an excellent electrocatalysis activity. Specific structure of Ni-Co/C could provide greatly efficient adsorption and desorption capacity to promote Cα–Cβ and Cβ–O bond cleavage. Therefore, in this electrocatalysis depolymerization process, the highest depolymerization rate exceeded 90%. And the yields (and conversion rates) of products (including benzaldehyde, acetophenone, benzoic acid, phenol) can reach to 124.08 mg/g (25.05%), 23.29 mg/g (4.15%), 44.64 mg/g (7.83%), 30.3 mg/g (6.9%). Furthermore, the electrocatalysis mechanism of Cα–Cβ and Cβ–O bond was investigated. The cleavage of Cα–Cβ and Cβ–O bond was initiated by in situ generated free radicals through Ni-Co/C. Then, the cleavage of Cα–Cβ and Cβ–O bond were occurred by ·OH and ·O2−. The results were showed that the Cα–Cβ bond cleavage was more in line with the β-C elimination and free radical pathways, and Cβ–O bond cleavage was consistent with direct oxidative addition. The enhanced electrocatalytic efficiency of the low-cost Ni-Co/C electrocatalyst combined with its good chemical stability and selectivity, which offer a promising route for developing an efficient lignin depolymerization technology.

Enhancing oxidation ability of graphitic carbon nitride photocatalysts to promote lignin Cα–Cβ bond cleavage in micellar aqueous media

As the most abundant aromatic resource, lignin is an appreciated biomass material to obtain aromatic high-value chemicals. However, the selective cleavage of lignin Cα–Cβ bonds under mild conditions constitutes a challenge. Herein, a photocatalyst having high oxidation capacity was successfully synthesized by codoping S and Cl atoms into graphite carbon nitride (g-C3N4). The resulting S,Cl/CN-1.5 photocatalyst exhibits enhanced photogenerated electron–hole separation ability and higher valence band potential than g-C3N4. S,Cl/CN-1.5 can efficiently break lignin Cα–Cβ bonds in micellar aqueous medium to produce benzaldehyde and benzyl alcohol as the main products. Mechanism studies show that the photocatalytic cleavage of lignin Cα–Cβ bonds proceeds via single-electron transfer and Cβ radical mechanisms in which hydroxyl radicals and photogenerated holes play an important role. Isotopic experiments show that the O atoms required for the photocatalytic cleavage of lignin Cα–Cβ bonds come from water in the micellar aqueous medium based on the full contact between water and substrate. Although O2 atmosphere is beneficial for the photocatalytic efficiency, O2 is not necessary for the photocatalytic cleavage of lignin Cα–Cβ bonds. This research provides a useful guide for designing efficient photocatalysts to depolymerize lignin into high-value chemicals.