JOURNAL OF CATALYSIS
·
2026
·
IF 6.5
Yishuang Wang,Lei Liu,Mingqiang Chen,Defang Liang,Chang Li,Jun Wang,Haosheng Xin
Lignin valorization is crucial for obtained sustainable fuels and chemicals, however its complex structure challenges efficient conversion. Herein, we designed a Ru-modified Co/attapulgite (CoRu x /ATP) catalysts for achieving the catalytic depolymerization of lignin (CDL) under ethanol coupled with H 2 medium to liquid fuel and guaiacols. CoRu 1 /ATP exhibited exceptional catalytic efficiency under optimal conditions, where the yields of liquid product and guaiacols reached 82.82 % and 584.67 mg/g, respectively. Experiments with model compounds demonstrated that the addition of Ru could effectively reduce the activation energy of the β-O-4 bond cleavage, which decreased from 78.6 kJ·mol −1 to 73.5 kJ·mol −1 . Characterization results indicated that the Ru additive yielded Co–Ru interfaces and its hydrogen spillover effect promoted the reduction of Co 3 O 4 to CoO and metallic Co (Co 0 ) to produce more oxygen vacancies (V O ). Additionally, the research on reaction mechanisms revealed V O and CoO phases in CoRu 1 /ATP enhanced the breakage of C–O bonds of lignin and the adjacent metallic Co and Ru sites and Co–Ru interfaces improved the activation of ethanol and molecular hydrogen into active hydrogen (H*) species to stabilize reactive intermediates and enhance hydrogenation reaction. The findings provide a potential method for directional lignin conversion.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Shinjae Lee,Hayoung Jeong,Hyungjin Choi,Chaewon Lee,Donghyeon Kim,Eonu Nam,Na Hye Kim,Hyeongeon Lee,Jeong Woo Han,Kwangjin An
Ru 1 /Mg(OH) 2 enables hydrogen-free catalytic fractionation of lignocellulose in water. • Single-atom Ru anchored on defect-rich Mg(OH) 2 forms active Ru–O–Mg sites. • C α –OH of β–O–4 linkages acts as an intrinsic hydrogen source for cleavage. • DFT reveals a low-barrier dehydrogenation-assisted β–O–4 scission pathway. • Up to 50.7 wt% aromatic monomers are produced without external hydrogen. Lignin-first biorefining offers a promising route for producing renewable aromatic chemicals; however, most reductive catalytic fractionation (RCF) strategies rely on external hydrogen, limiting their scalability and safety. Here, we report a Ru 1 /Mg(OH) 2 catalyst that enables self‑hydrogen supplied catalytic fractionation (SCF) of lignocellulose in water without external H 2 . The catalyst delivers a remarkably high lignin monomer yield of 50.7 wt% from birch sawdust, approaching the theoretical maximum. Comprehensive characterization (XRD, TEM, XAFS, XPS, Raman, and ESR) reveals that Ru is predominantly atomically dispersed on Mg(OH) 2 and interacts strongly with proton-missing oxygen defects to form unique Ru–O–Mg interfacial sites. These sites generate highly basic oxygen species that promote C α –OH dehydrogenation and subsequently facilitate β–O–4 bond cleavage. Model compound studies confirm that the C α –OH group serves as the intrinsic hydrogen donor, while isotope-labeling experiments and kinetic analysis identify C α –H activation as the rate-determining step. Density functional theory calculations further establish that the dehydrogenation-assisted β–O–4 cleavage pathway has the lowest activation barrier (0.31 eV), validating the endogenous hydrogen mechanism. Collectively, this study provides fundamental insights into hydrogen-free lignin depolymerization and establishes Ru 1 /Mg(OH) 2 as a highly efficient platform for green and scalable lignocellulose valorization. Lignin-first biorefining offers a promising route for producing renewable aromatic chemicals; however, most reductive catalytic fractionation (RCF) strategies rely on external hydrogen, limiting their scalability and safety. Here, we report a Ru 1 /Mg(OH) 2 catalyst that enables self-hydrogen supplied catalytic fractionation (SCF) of lignocellulose in water without external H 2 . The catalyst delivers a remarkably high lignin monomer yield of 50.7 wt% from birch sawdust, approaching the theoretical maximum. Comprehensive characterization (XRD, TEM, XAFS, XPS, Raman, and ESR) reveals that Ru is predominantly atomically dispersed on Mg(OH) 2 and interacts strongly with proton-missing oxygen defects to form unique Ru–O–Mg interfacial sites. These sites generate highly basic oxygen species that promote C α –OH dehydrogenation and subsequently facilitate β–O–4 bond cleavage. Model compound studies confirm that the C α –OH group serves as the intrinsic hydrogen donor, while isotope-labeling experiments and kinetic analysis identify C α –H activation as the rate-determining step. Density functional theory calculations further establish that the dehydrogenation-assisted β–O–4 cleavage pathway has the lowest activation barrier (0.31 eV), validating the endogenous hydrogen mechanism. Collectively, this study provides fundamental insights into hydrogen-free lignin depolymerization and establishes Ru 1 /Mg(OH) 2 as a highly efficient platform for green and scalable lignocellulose valorization. Download: Download high-res image (237KB) Download: Download full-size image
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Journal of Environmental Chemical Engineering
·
2026
·Vol. 14
·期 3
·122374
·
IF 7.5
Feng Chen,Xiang Xia,Wei Chen,Wei Liu,Xinxin Liao,Lei Xiong,Yanqiao Jin
Refining lignin and its derivatives into biofuels and fine chemicals via catalytic transfer hydrogenation (CTH) has gained significant attention for its potential in utilizing renewable resources and reducing fossil fuel dependence. Herein, a series of bimetallic Cu-Co catalysts with varying metal ratios are synthesized via a facile hydrothermal method and successfully applied in the efficient CTH of the α-O−4 model compound benzyl phenyl ether (BPE) and corncob lignin. Cu 0.5 Co 1 @CN has the best performance among catalysts with different CuCo ratios due to the formation of the CuCo 2 O 4 phase which provides more acid sites and hydrogen adsorption/desorption sites. Under the reaction conditions of 190 °C in isopropanol, the Cu 0.5 Co 1 @CN catalyst achieves the complete conversion of BPE to cyclohexanol and toluene, and demonstrates excellent CTH performance towards other α-O−4 and β-O−4 model compounds. This catalyst simultaneously enables the demethoxylation and hydrogenation of phenolic compounds like guaiacol. Furthermore, Cu 0.5 Co 1 @CN efficiently converts corncob lignin, producing a high proportion of phenolic compounds in the resulting liquid (88.26%), while preventing the aromatic hydrocarbons from being hydrogenated. Overall, this work provides a novel and effective strategy for transforming lignin into high-value products.
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高影响因子
JOURNAL OF CATALYSIS
·
2026
·
IF 6
Meng Liu,Jianhao Qiu,Guanglu Xia,Lu Zhang,Chen Chen,Qian Liu,Jianfeng Yao
Efficient and selective cleavage of C–C bonds in lignin remains a critical hurdle for its sustainable valorization into aromatic chemicals. Herein, we rationally construct a Z-scheme heterojunction photocatalyst by integrating phosphorus-doped graphitic carbon nitride (P-CN) with rod-like Bi 2 O 3 derived from a bismuth metal–organic framework (Bi-MOF). Phosphorus doping effectively modulates the band structure of g-C 3 N 4 , broadening visible-light absorption and enhancing its reduction capacity. Notably, Bi-MOF serves a dual function: it acts as the precursor for rod-like Bi 2 O 3 while simultaneously functioning as a pore-generating agent. Its decomposition during thermal treatment imparts substantial mesoporosity to the overlying g-C 3 N 4 nanosheets, dramatically increasing the specific surface area of the heterojunction. This mesoporous architecture and high surface area facilitate lignin diffusion and oxygen capture, thereby promoting the generation of carbon-centered radical intermediates and singlet oxygen—the key reactive species driving lignin C α –C β bond cleavage. Consequently, the optimized P-CN/Bi 2 O 3 catalyst achieves 97.5% conversion of the lignin model compound, 2-phenoxy-1-phenylethanol, and 94.3% benzaldehyde yield under 405 nm light irradiation, drastically outperforming pristine Bi 2 O 3 (31.4% conversion, 30.5% yield) and P-CN (55.8% conversion, 50.9% yield). This work highlights the untapped potential of MOF-derived materials in morphological engineering, offering new design principles for high-performance photocatalytic systems toward sustainable lignin valorization.
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高影响因子
ACS Sustainable Chemistry & Engineering
·
2026
·Vol. 14
·期 29
·13042-13055
·
IF 7.6
Lau Chun-Yin,Li Xinwei,Zhang Yanlin,Rangarajan Goutham,Tse Ho-Yin,Zhuang Huichuan,Leu Shao-Yuan,Farnood Ramin R.
In this study, an amorphous carbon-rich carbon nitride photocatalyst was prepared by nitric acid treatment of pyrolyzed melamine followed by nitrogen annealing. The resulting semiconductor material exhibited an up-shifted valence band that enhances the oxidizing power of photogenerated holes, enabling selective C α −C β bond cleavage of 2-phenoxy-1-phenylethanol (2-POE). Using 1.5 g L −1 of the optimized photocatalyst in acetonitrile, 2-POE underwent first-order conversion with a reaction rate of 2.55 h −1 under a 9 W blue LED light source. Product analysis showed the formation of benzaldehyde as the major product, confirming C−C bond scission with 93.1% selectivity. In addition, ring-opening reactions were observed, producing fumaric and maleic acids as the by-products. Photocatalytic depolymerization of organosolv lignin further demonstrated ring opening of the β-O-4 linking motifs, forming dicarboxylic acids analogous to those generated from 2-POE. These demonstrate a metal-free photocatalytic platform capable of promoting β-O-4 bond cleavage in lignin model compounds and inducing photocatalytic structural modification of organosolv lignin, accompanied by the formation of low-molecular-weight aliphatic dicarboxylic acids.
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ENERGY & FUELS
·
2026
·Vol. 40
·期 33
·18068-18080
·
IF 6
Fu Zong-Pin,Zhao Yun-Peng,Wu Yu-Fa,Qiu Le-Le,Liu Fang-Jing,Zhong Mei,Liang Jing,Cao Jing-Pei
Efficient depolymerization of lignite remains challenging
owing
to both its structural complexity and the high stability of oxygen-containing
bridge linkages. Herein, low-temperature pyrolysis and oxidative pretreatments
were employed to regulate oxygen-containing structures and enhance
the hydrogenolysis reactivity of Zhaotong lignite (ZT). These pretreatments
promoted the structural evolution of lignite, activated oxygen-containing
bridge structures, and suppressed the recondensation of reactive intermediates,
thereby facilitating subsequent depolymerization reactions. A CuCoOx
catalyst capable of dynamic in situ reconstruction was introduced
for catalytic hydrogenolysis. Under reaction conditions, partial reduction
of CuCoOx generated reconstructed Cu 0 -CoOx interfacial
active sites, where the synergistic interaction between metallic Cu
and defect-rich CoOx promoted H 2 activation and selective
C–O bond cleavage. Density functional theory (DFT) calculations
further revealed that interfacial electron redistribution at the Cu
cluster/Vo-Co 3 O 4 (311) interface facilitated
H 2 activation and stabilized reactive hydrogen species.
These findings provide new mechanistic insights into pretreatment-regulated
and interface-controlled hydrogenolysis pathways for the efficient
valorization of low-rank coal.
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Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Chengcheng Suo,Xiaochang Zhang,Xinai Li,Jifang Zhang,Hongru Zhang,Rui Teng,Wei Li,Sha Luo,Bing Tian,Qingjiang Pan,Chunhui Ma,Zhijun Chen,Shouxin Liu
In lignin depolymerization, we use a lot of organic solvent which is still an environment problem in large scale industrialization. Therefore, we propose the photocatalytic biorefining green closed-loop (PBGC) to realize green and sustainable development. Different from organic solvents, we find that supramolecular solvents can synergistically interact with photocatalysts to influence the final products. The solubility of Alkali lignin (AL) in supramolecular solvent was 150 % higher than in ChCl/1,4 BDO (1:3) due to the AL and solvent have the similar supramolecular structure. Additionally, supramolecular solvent was used at low temperature (60 °C) which overcame the bottleneck of high viscosity provided huge possibility on industrial application. AL was photocatalytic-assisted oxidized by WO 3 /g-C 3 N 4 /h-BN (WCB). The conversion of AL achieves 38.61 wt%, and the yield of vanillic acid is 22.87 % in product. In this process, the β-O-4 bonds within the lignin structure were activated by hydroxyl radicals originating from the supramolecular solvent. The hydroxyl radical was produced from 1,4 BDO in supramolecular solvent. In dark environment, AL interacted with supramolecular solvent aroused the generation of C α aryloxy radical (ArO•). The superoxide radical was produced on the WCB from O 2 which could stabilize the C α ArO• quickly to final products.
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高影响因子
FUEL
·
2022
·
IF 8.035
Mingqiang Chen,Wei Dai,Yishuang Wang,Zhiyuan Tang,Hong Li,Chang Li,Zhonglian Yang,Jun Wang
Lignin catalytic depolymerization (LCD) into liquid fuels and aromatic chemicals in supercritical ethanol systems is one of the most effective strategies for efficient utilization of biomass resources. In this study, a series of sepiolite (SEP) supported Mo-Mn catalysts with different Mn/Mo ratios were prepared and applied to LCD. Experimental results for lignin and 2-phenoxy-1-phenyl ethanol (PP) confirmed that Mo/Mn species promoted the breakage of β-O-4 bonds, Mn additive effectively inhibited the alkylation of intermediates, and Mn/Mo ratios distinctly affected the yields of lignin oil (LO) and guaiacols. All as-prepared Mn-Mo/SEP catalysts achieved approximately 100 % conversions of lignin and PP. Various characterization results demonstrated that Mn/Mo ratios could regulate the particle sizes of metal oxides as well as the concentration of oxygen vacancies (O V ) and surface acidic sites. In 3Mn1Mo/SEP, the appropriate interaction among SEP , Mn and Mo species reduced the particle sizes of metal oxides and rendered the crystalline phase structure in a relatively complex state, which undoubtedly generated massive steps/corners on its surface and then enhanced the hydrogenation reaction. Furthermore, the 3Mn1Mo/SEP contained many O V and suitable distribution of Lewis and Brønsted acid sites, which facilitated the adsorption of oxygen-containing intermediates and further hydrogenation and deoxygenation. Therefore, 3Mn1Mo/SEP achieved 45.7 % of LO yield with an HHV of 32.31 MJ/Kg and the highest selectivity to phenols (85.61 %) and yield of guaiacols (308.9 mg/g lignin). In addition, the plausible reaction network for LCD was proposed based on the results of experiments and characterizations.
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高影响因子
Surfaces and Interfaces
·
2022
·
IF 6.137
Jin-Yu Wang,Zhong-Zhu Hu,Xin-Ting Sun,Ya-Qin Gao,Jun-Lin Wang,Jie Xu,Gan Jin
Photocatalytic cleavage of lignin C β -O-4 bonds is a very effective method to promote the high-value utilization of lignin because lignin can provide a large number of aromatics. However, the higher carrier recombination rate severely inhibits the efficiency of photocatalytic cleavage of C β -O-4 bonds in lignin model compound. Here, heterojunction photocatalysts CdS-C 3 N 4 were successfully synthesized through the photodeposition of different masses of CdS on the surface of C 3 N 4 . The obtained photocatalyst CdS-C 3 N 4 can effectively break the lignin C β -O-4 bonds in 2-Phenoxy-1-phenylethanol (lignin model compound) and the products formed are mainly phenol (Phol) and acetophenone (Ap). More importantly, the yields of Phol and Ap were up to 86.5% and 74.3%, after only irradiation for 1.5 h, respectively, under optimum conditions. A mechanistic study showed that photocatalytic reaction follows a photogenerated electron-hole coupled mechanism. The high photocatalytic performance of CdS-C 3 N 4 is mainly ascribed to the fast photogenerated electron-hole separation capability and good dispersion of CdS on C 3 N 4 . This work offers an idea for selective cleavage of lignin C β -O-4 bonds by constructing a heterojunction photocatalyst.
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高影响因子
FUEL
·
2022
·
IF 8.035
Jia-Pei Guo,Fang-Jing Liu,Lei-Lei Bie,Xing-Gang Si,Yan-Hong Li,Ping Song,Nian Liu,Yun-Peng Zhao,Zai-Xing Huang,Jing-Pei Cao,Xian-Yong Wei
The utilization of lignin to produce high value-added chemicals is conducive to alleviating the fossil energy crisis. Herein, Ni nanoparticles supported on iron/nitrogen co-doped carbon was prepared by co-pyrolysis and solvothermal reduction method for catalytic hydrogenolysis (CH) of dealkaline lignin and its model compounds. The catalysts were prepared under different calcination temperature, N/C ratio and Ni loading, and the optimal catalyst was Ni 10% @Fe/NC 0.33 – 800 (calcination temperature: 800 °C, N/C ratio: 0.33, Ni loading: 10%) based the on the CH of benzyl phenyl ether (BPE). Ni 10% @Fe/NC 0.33 – 800 showed good catalytic performance on the selective cleavage of C-O bond of lignin and its model compounds. The BPE conversion reached up to 97.7% over Ni 10% @Fe/NC 0.33 – 800 under mild conditions (230 °C, 1 MPa H 2 , and 0.5 h) with toluene and cyclohexanol as major products. Catalyst characterizations suggest that N content affects the formation of NiFe alloy and the synergistic effect between Ni and Fe plays an important role in CH of BPE. Moreover, Ni 10% @Fe/NC 0.33 – 800 could promote the cleavage of C-O bonds in dealkaline lignin through CH and hence enhance producing aromatics such as phenols, aromatic ethers, and aromatic esters, among which phenols are the main aromatics with guaiacols predominant.
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高影响因子
FUEL
·
2020
·
IF 5.578
Shanshuai Chen,Qiqi Lu,Wanying Han,Puxiang Yan,Hongliang Wang,Wanbin Zhu
Recently, a two-step strategy involving oxidative activation and reductive depolymerization becomes very popular for lignin conversion. However, both positive and negative results are obtained, and the detailed mechanism is still unknown. This study thoroughly investigated the effects of several key factors, including hydrogen pressure, reaction temperature, and catalyst compositions, on the reductive conversion of oxidized lignin (lignin OX ) to aromatics. For lignin oxidative activation, FT-IR, 2D NMR, and TG/DTG were used to prove that hydroxyl groups at lignin side chains had been successfully oxidized to carbonyl groups by AcNH-TEMPO/HNO 3 /HCl system. For lignin OX reductive conversion, pathways and mechanisms were explored, and the applicable conditions of this strategy were determined. Under relative moderate hydrogen pressure (e.g. 2 Mpa) over metal–acid catalysts, e.g. Ru/γ-Al 2 O 3 combined with Hf(OTf) 4 ), an obvious advantage of lignin OX conversion was found. Yield of valuable product from lignin OX was 42.98% which was much higher than that (10.99%) from unoxidized lignin. While, under high hydrogen pressure or promoted by catalysts with high hydrogenation activities, lignin OX tended to be reconverted to original lignin structures with loss of its conversion advantage. 2-phenoxyacetophenone as a lignin OX model was used to verify this speculation and to predict reaction pathways over different catalytic systems. These results proved that a catalyst with both hydrogenolysis and hydrolysis activity was essential for efficient lignin OX depolymerization.
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高影响因子
FUEL
·
2019
·
IF 5.128
Wenjing Song,Weikun Lai,Yixin Lian,Xingmao Jiang,Weimin Yang
Catalytic transformation of lignin is a sustainable way to provide aromatics, which depends on the structure and property of catalytic sites. A bifunctional sulfated ZrO 2 supported CoMo sulfide catalyst has been synthesized by in situ exsolution approach. The exsolved CoMo-sZr(exs) catalyst significantly enhanced the initial C–O bond cleavage rate (0.058 mol·g −1 ·h −1 ) compared to the impregnated and physically mixed sulfated ZrO 2 supported CoMo sulfide catalysts. Notably, the reusability tests also showed that the as-prepared catalyst presented total ethers conversion of 94% with aromatics yield of 86% after four consecutive cycles. This was related to the appropriate sulfide-support interaction, acid sites and highly-dispersed CoMo sulfide, in conformity with the catalyst characterization. Thereby it could facilitate reactant adsorption and effectively break down the C–O bonds in lignin derived fragments to form aromatics. This work points out a new avenue for the design of effective bifunctional catalysts for lignin depolymerization.
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高影响因子
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