CHEMICAL ENGINEERING JOURNAL
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2023
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IF 15.1
Fei Ge,Haihong Xia,Jing Li,Yaqi Xue,Jiantao Su,Xiaohui Yang,Jianchun Jiang,Minghao Zhou
Catalytic upgrading lignin-derived bio-oil with high oxygen content to directly usable transport fuel through hydrotreatment is highly desirable, but still remains a challenge. In this work, a series of Co-based catalysts were synthetized using metal–organic frameworks (MOFs) as a structure-directing agent and lignin as a renewable carbon precursor via a simple hydrothermal method. Among these catalysts, Co/C-EL-0.5–500 showed the best catalytic hydrotreatment activity, affording 100% guaiacol conversion with 90% cyclohexanol yield under the conditions of 240 °C, 0 MPa N 2 and 4 h. According to the characterization results of XRD, SEM, TEM, BET, ICP, NH3-TPD and XPS, the excellent performance of Co/C-EL-0.5–500 was attributed to large specific surface area, small Co particle size, and optimal acidity. The possible reaction pathway was proposed based on the product distribution. In addition, isopropanol was used as H-donor instead of extra hydrogen, and we hope that it could provide a novel strategy for bio-oil upgrading.
研究领域:
化学工程
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可再生能源
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催化科学
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DOI
高影响因子
Journal of Environmental Chemical Engineering
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2025
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IF 7.2
Peng Gao,Min Zheng,Mengni Zhou,Yiwei Ma,Guirong Bao,Chengyan Wang
The valorization and toxicity reduction of phenolic substances are critical challenges for achieving green and sustainable development in the petroleum, coal, and biomass industries. This study investigated the phenolic model compound guaiacol hydrodeoxygenation over Ru/Al 2 O 3 catalysts, demonstrating that synthesis within an anaerobic glovebox significantly enhances catalytic activity compared to ambient synthesis. Four solvents (ethanol, methanol, tetrahydrofuran, and n-dodecane) were evaluated for their impact on guaiacol conversion and product distribution. Experimental results demonstrated that non-polar n-dodecane achieved 100 % guaiacol conversion and 92.8 % cyclohexane selectivity, attributed to weak catalyst-solvent interactions verified by first-principles calculations. Reaction optimization enabled > 90 % yields of 2-methoxycyclohexanol, cyclohexanol, and cyclohexane. Crucially, a novel low-temperature demethoxylation pathway via the intermediate 2-methoxy-1-cyclohexen-1-ol was identified through quantum chemistry calculations, offering a strategy to enhance cyclohexanol production. Kinetic analysis revealed apparent activation energies of 55 kJ/mol (demethoxylation) and 72 kJ/mol (dehydroxylation). The catalyst maintained stable performance over five cycles. These findings underscore the critical importance of catalyst synthesis, solvent environment, and reaction control in achieving efficient and selective guaiacol hydrodeoxygenation, offering strategies for green valorization and toxicity reduction of phenols.
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DOI
高影响因子
CARBON
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2025
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IF 11.6
Jing-jing Wu,Jia-yuan Tian,Feng Lin,Yu-long Ma,Yong-gang Sun
The catalytic conversion of lignin-derived monomer guaiacol to cyclohexanol is pivotal for the development of emerging biofuels. However, designing highly selective hydrodeoxygenation (HDO) catalysts for this process remains challenging. In this study, a Mott-Schottky catalyst comprising nitrogen-doped carbon-encapsulated cobalt NPs (Co@NC) was prepared by pyrolyzing the ZIF-67 precursor, and its catalytic mechanism in the conversion of guaiacol was elucidated. A series of characterizations revealed that nitrogen atom doping induced electron migration from the cobalt core to the carbon layer, thereby precisely regulating the electron density distribution of both the carbon shell and cobalt active sites. Activity experiments combined with density functional theory (DFT) calculations indicated that the reconstructed electronic structure optimized the adsorption capacity for guaiacol and hydrogen, Enabling complete substrate conversion and efficient cyclohexanol production under mild conditions. Compared with traditional catalysts such as nitrogen-doped carbon-supported cobalt (Co/NC) and carbon-encapsulated cobalt (Co@C) catalysts, the excellent performance of Co@NC underscores the critical regulatory role of the electron migration effect in enhancing selective HDO activity. This work provides a novel design strategy focused on electronic structure for optimization the high-value conversion of lignin-derived compounds.
研究领域:
催化化学
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材料科学
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化学工程
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物理化学
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可再生能源
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产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
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2024
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IF 7.7
Rongji Li,Guangyuan Shi,Lichuan Chen,Yun Liu
In this study, a purposefully formulated ternary deep eutectic solvents (DESs), consisting of choline chloride, guaiacol, and lactic acid in a molar ratio of 1:1:1, was synthesized for the extraction of polysaccharides from Ganoderma lucidum . The physicochemical properties of the synthesized DESs, including viscosity, density, pH, and hydrogen bonds, were comprehensively examined. Verification of the formation of the ternary DESs was accomplished through Fourier transform infrared and Nuclear magnetic resonance spectroscopies. Subsequently, response surface methodology was applied to optimize crucial parameters for polysaccharide extraction using DESs, resulting in a maximal extraction yield of 94.72 mg/g under the optimized conditions. Cyclic experiments demonstrated the commendable cyclic stability of the DESs, with a recovery rate exceeding 88 %. Furthermore, experiments on monosaccharide composition, molecular weight, and antioxidant activity of the isolated polysaccharides were conducted. Density functional theory was employed to gain insights into the molecular mechanism of polysaccharide extraction by DESs. The findings revealed a triple hydrogen bond interaction and a high binding energy (65.29 kcal/mol) between the DESs and glucose, highlighting their significant contribution to the high extraction effectiveness. This molecular-level understanding underscores the inherent superiority of DESs in the polysaccharide extraction processes, providing valuable insights for future applications in this field.
研究领域:
食品科学
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生物化学
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产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS A-GENERAL
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2024
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IF 4.7
Wenqin Zhao,Zonghao Zhang,Bo Wang,Yang Lv,Lei Huang,Pingle Liu
Catalytic hydrodeoxygenation is a plausible route to upgrade the quality of biomass energy sources. Herein, a series of Ru-Co alloy catalysts (Ru-Co/TiO 2 -Al 2 O 3 ) were prepared and applied in guaiacol hydrodeoxygenation to cyclohexanol. It was found that Ru-Co nanoparticles with average size of about 8.67 nm were uniformly dispersed on TiO 2 -Al 2 O 3 support. It was verified that Co doping led to the formation of electron-rich Ru and hence promoted the desorption of active hydrogen, while the constructed TiO 2 -Al 2 O 3 support possessed abundant oxygen vacancies and acidic sites, which facilitated adsorption and hydrogenolysis of −OCH 3 functional group. 5Ru-5Co/TiO 2 -Al 2 O 3 catalyst gives the best catalytic performance of >99% guaiacol conversion and 94% selectivity to cyclohexanol. In addition, the strong interactions between Ru-Co nanoparticles and TiO 2 -Al 2 O 3 could significantly inhibit aggregation and leaching of Ru-Co nanoparticles during the reaction. The research results will provide reference to design highly efficient and stable bimetallic catalysts in converting lignin-derived bio-oils.
研究领域:
催化化学
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生物质能
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DOI
高影响因子
ACS Catalysis
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2026
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IF 13.6
Xin Han,Shanguang Xu,Fan Zhang,Ruiying Chai,Shanguo Du,Xiuling Jiao,Dairong Chen,Jie Zhang
The modulation of catalyst surfaces with alkali metals is a key research topic in heterogeneous catalysis. This study elucidates the mechanistic role of sodium promotion in enhancing the performance of MgO-supported Pt catalysts for the selective hydrodeoxygenation (HDO) of guaiacol to phenol. The catalytic activity exhibited a distinct volcano-shaped trend as a function of sodium content, with optimal performance achieved using the Pt-5Na/MgO catalyst. Under the conditions of 280 °C and 0.1 MPa H2 pressure, the Pt-5Na/MgO catalyst achieved 98% conversion and 91% phenol selectivity. Mechanistic studies revealed that sodium modification increased the basicity of the support, and a correlation was observed between guaiacol conversion and the density of surface basic sites. Additionally, sodium addition induced electronic restructuring of the catalyst by transferring electrons from Na to Pt, which increased the electron density of Pt nanoparticles, facilitated the reduction of Pt, and generated more catalytically active Pt species. This electronic modification enhanced the hydrogen activation capacity of Pt species, while the stabilization of hydrogen species on basic sites enhanced hydrogen spillover efficiency, thereby increasing the availability of reactive hydrogen species. The findings provide insight into the design of alkali-metal-promoted Pt catalysts for hydrogenation applications.
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DOI
高影响因子
BIOMASS & BIOENERGY
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2022
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IF 5.774
Yanlin Xu,Zhuoyi Liu,Bin Liu,Bin Dong,Yichuan Li,Yanpeng Li,Hailing Guo,Yongming Chai,Chenguang Liu
Pulping black liquor is a serious source of water pollution worldwide, which is very difficult to subsequently treat. Lignin is the main component of the black liquor and is the only natural aromatic recyclable resource, which is burnt as waste in the Kraft pulping industry. Designing an efficient lignin conversion catalyst that suitable for the strong alkaline environment of black liquor harbors tremendous carbon-neutral potential but still remains a scientific and technological challenge. In this work, the strong alkaline environment of black liquor was simulated, and low-cost pretreated Ni/AC catalysts were adopted to the hydrodeoxygenation (HDO) of a lignin model (guaiacol), and a breakthrough was achieved in the efficient transformation of lignin compound into hydrocarbons. By multitechniques, (e.g., FT-IR, XPS , Boehm titration, HRTEM), the relevance between introducing functional acid groups and the surface properties of catalysts was revealed. It is found that the increased acidic groups are responsible for the enhanced C (sp2) -O cleavage reactions, while improving the dispersion of Ni NPs and thus enhance the HDO efficiency. It is worth noting that better selectivity of benzene and lower hydrogen consumption are achieved on Ni/NOAC during the HDO process. Furthermore, the reaction routes of guaiacol on catalysts with different functional acid groups were proposed. This work provides guidance for efficient utilization of lignin in waste black liquor, and is of great significance to the development of sustainable carbon-neutral biorefinery and environmental protection.
研究领域:
化学工程
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环境科学
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生物能源
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DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
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2022
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IF 8.129
Huiyan Zhang,Chenjun Yang,Yujie Tao,Min Chen,Rui Xiao
The unstable oxygenates of raw bio-oil limit its high-value utilization, which renders the refinement process necessary. Catalytic cracking is one of the promising refining methods and HZSM-5 was found to be an effective catalyst. To investigate the reaction mechanism of catalytic cracking of the oxygenated components in bio-oil, guaiacol and acetic acid, are employed for the catalytic conversion over HZSM-5 and metal modified zeolite Zn/HZSM-5 in a self-designed micro-reactor. Herein, the mechanism of pyrolysis and catalytic cracking was calculated by density functional theory (DFT). For guaiacol, the selectivity of salicylaldehyde decreased from 57.41% to 41.84% and 40.31% over HZSM-5 and Zn/HZSM-5, respectively. In the catalytic cracking over Zn/HZSM-5, the yield of aromatic hydrocarbon increased. More specifically, benzene appeared in the liquid product. For acetic acid, the removal of the oxy-functional group was further promoted by Zn/HZSM-5, the as-formed ketene intermediate continues to react with zeolite catalysts, generating acetyl cation, and finally formed CO and ethylene. Zn/HZSM-5 has a better effect on promoting the reaction of ketene and methoxide since the energy barrier of the rate-determining step in this reaction decreased from 163.27 kJ/mol to 151.19 kJ/mol. Demethoxylation and dehydration were considered to be favored by Lewis acid sites.
研究领域:
化学工程
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能源科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
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2023
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IF 4.7
Yong Liu,Xinghua Zhang,Lungang Chen,Jianguo Liu,Qi Zhang,Longlong Ma
This study explores the efficacy of a cost-effective Cu-ZnO-Al 2 O 3 catalyst for one-pot hydrodeoxygenation of guaiacol into hydrocarbons. Notably, complete conversion of guaiacol was achieved, yielding a 99.6% hydrocarbon over the robust Cu(6)Zn(3)Al(1) catalyst under the conditions of 4 MPa H 2 , 300 °C, and 8 h with a catalyst/guaiacol ratio of 0.5 g/1.0 g. In-depth catalyst characterizations unveiled the presence of oxygen vacancies within the ZnO surface layer, acting as pivotal active sites that facilitated the hydrodeoxygenation of guaiacol. Furthermore, Density Functional Theory (DFT) calculations were employed to evaluate several potential active sites, revealing that the oxygen vacancy of ZnO on the Cu surface played a crucial role. This vacancy enhanced the adsorption of intermediate cyclohexanol and markedly reduced the energy barrier for the rate-limiting step. This comprehensive investigation sheds light on the catalytic pathway and offers insights into designing efficient and sustainable biofuel production processes.
研究领域:
催化
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化学工程
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材料科学
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能源
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产品关联
DOI
高影响因子
Journal of Environmental Sciences
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2025
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IF 6.3
Jiayi Wang,Rui Zeng,Jun He,Chengjun Wang
The mechanisms and kinetics of the formation of aqueous secondary organic aerosol ( aq SOA) via photosensitive water-soluble matters (WSM) mediated photo-aging process of dissolved methoxyphenols, using guaiacol (GUA) as a model compound, in sunlit atmospheric aqueous phase were investigated. The occurrences and optical indices of typical photosensitive WSM, including both water-soluble inorganic matter (WSIM) and water-soluble organic matter (WSOM), in aqueous aerosol extracts were characterized and determined by using a variety of instrumental techniques. The results shown that various photosensitive WSIM and WSOM occur in atmospheric aqueous aerosol. The photolysis of WSM can generate abundant reactive oxygen species (ROS) and 3 WSOM*, which play equally important roles in entire GUA transformation process leading to aq SOA formation. Of those, the 3 WSOM* is the predominant contributor for initial GUA transformation due to its high [ 3 WSOM*] ss of 5.35 ± 0.12 × 10 −13 mol/L, generation rate of 3.43 × 10 −7 mol/(L·s), quantum yield of 4.86 %, and the rate constant of reaction with GUA over ∼10 9 L/(mol·s). Meanwhile, the ROS are key reactive species reacting with soluble intermediates of GUA transformation to produce final insoluble substances such as ether and low-volatile phenols, which are major constituents of formed aq SOA in aqueous extracts of aerosols. This work sheds the deeper insights into the mechanisms and kinetics on aq SOA formation via indirect phototransformation of dissolved methoxyphenols in real atmospheric aqueous phase.
研究领域:
大气化学
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环境科学
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光化学
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气溶胶科学
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产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
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2025
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IF 6.5
Xin Han,Shanguang Xu,Fan Zhang,Ruiying Chai,Shanguo Du,Xiuling Jiao,Dairong Chen,Jie Zhang
Modulation of the surface properties on catalyst support for selective hydrogenation with high activity and selectivity is a significant but challenging topic. Herein, we report the promotion of basic sites on MgO surface on the selective hydrodeoxygenation (HDO) of guaiacol to phenol. The results showed that basic MgO support could inhibit the further breaking of C–O bond of generated phenol compared to acidic support, which facilitated the formation of phenol with high selectivity. The catalytic activity of Pt/MgO catalysts was markedly influenced by the concentration and types of basic sites on the catalyst surfaces. The increase in the concentration of basic sites on the catalysts surface led to a linear increase in the conversion of guaiacol, and the selectivity (92 %) of phenol was achieved with >99 % conversion at the conditions of 280 °C and 0.1 MPa H 2 pressure. The characterization of catalysts, combined with the kinetic analysis, demonstrated that the strong basic sites generated by isolated O 2− species on the MgO surface could significantly enhance the adsorption of guaiacol, and improve the dispersion and electronic density of Pt species through the interaction of basic sites and Pt species, thereby further promoting the hydrogen dissociation, which achieved the excellent catalytic performance and stability by the dual active sites of basic sites and Pt sites. This study provides a promising strategy for the design of supported metal catalysts with improved surface basic sites for the selective HDO reactions of oxygenates.
研究领域:
催化化学
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绿色化学
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生物质转化
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多相催化
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可再生能源
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产品关联
DOI
高影响因子
JOURNAL OF VINYL & ADDITIVE TECHNOLOGY
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2025
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IF 3.6
Huajun Duan,Ruian Li,Yuan Gao,Jiangtao Geng,Yuan Chen,Ya Li,Weipeng Liu,Huiru Ma
Epoxy resin (EP) is a thermosetting resin of significant commercial value. However, it is afflicted by inherent defects, including flammability and non-self-extinguishing properties. Consequently, it is imperative to modify EP with flame retardant additives. Currently, the majority of flame retardants are characterized by complexity and a cumbersome preparation process, which is not conducive to environmental sustainability. Consequently, there is a growing demand for eco-friendly bio-based flame retardants. In this paper, bio-based reactive flame retardants (HGD) with hydroxymethyl and phenolic hydroxyl groups were prepared in a one-step method by bulk reaction using the bio-based materials 5-hydroxymethylfurfural, guaiacol, and DOPO as raw materials, and were added into EP as co-curing agents to prepare flame retardant epoxy resins (FREPs). Comprehensive evaluation revealed fire safety improvements in HGD-modified EP systems. Specifically, the optimized EP/HGD-7.5 formulation demonstrated reductions in key combustion parameters compared to unmodified EP: 35.7% decrease in peak heat release rate (pHRR), 34.0% reduction in total heat release (THR), 24.3% lower average effective heat of combustion (Av-EHC), and 16.8% suppression of total smoke production (TSP). Meanwhile, the modified composites exhibited concurrent mechanical enhancement. At 7.5% HGD loading, flexural strength and modulus increased by 21.1% and 20.0%, respectively, while tensile performance optimization occurred at 5.0% loading with 20.6% strength improvement and 24.5% modulus elevation. Notably, HGD-modified EP systems maintained superior thermal stability. The glass transition temperature ( T g ) of EP/HGD-7.5 is 154.2°C, exceeding that of EP. This investigation successfully demonstrates a sustainable approach for developing multifunctional epoxy composites with enhanced fire resistance and mechanical performance through bio-based modification.
研究领域:
高分子科学
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材料工程
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消防安全工程
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绿色化学
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可持续材料
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）