RENEWABLE ENERGY
·
2026
·
IF 9.1
Jianan Liu,Wei Wang,Xinran Ji,Aimin Li,Lei Zhang
Efficient conversion of lignocellulosic biomass into furan-based chemicals is crucial for sustainable biorefineries. This study presents a synergistic catalytic system combining ferric chloride (FeCl 3 ) with a γ-valerolactone (GVL)/H 2 O co-solvent, revealing the pivotal role of trace water in enhancing furfural production. Under optimized conditions (H 2 O:GVL = 2:28, 180 °C), the system achieved an apparent furfural yield of 109.5 %, calculated based on the theoretical furfural yield from the xylan content of corncob. Mechanistic insights elucidated that Fe 3+ disrupts biomass–solvent interactions, thus facilitating hemicellulose and cellulose depolymerization. The significant 5-HMF yield highlights the system capacity to effectively hydrolyze cellulose into glucose and subsequently convert it via Fe 3+ -catalyzed aldose–ketose isomerization and dehydration pathways. Isotopic labeling with [1– 13 C] and [6– 13 C] glucose confirmed that Fe 3+ catalyzes aldose–ketose isomerization, a critical step steering sugar conversion toward furanic compounds. Furthermore, 2D-HSQC NMR and TG-FTIR-GC/MS analyses revealed that the FeCl 3 –GVL/H 2 O system promoted lignin depolymerization into low-molecular-weight aromatics for enhancing lignin valorization. Together, these findings reveal that trace water lowers the activation energy to accelerate sugar release and modulates the hydrogen-bonding network to stabilize furfural, while the GVL-rich phase stabilizes reactive intermediates, suppressing side reactions and improving furfural selectivity. Compared to conventional mineral acid systems, the FeCl 3 –GVL/trace-water system offers superior selectivity and efficiency under optimized conditions for biorefinery of lignocellulosic biomass.
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DOI
高影响因子
Small
·
2026
·
IF 11.8
Guanhua Cheng,Yunfei Ran,Yalong Liu,Jiameng Sun,Xiangyu Fei,Zhenhan Li,Dongshang Ma,Zhiyong Feng,Chunyan Qiao,Tianyi Kou,Zhonghua Zhang
The development of efficient electrocatalysts for biomass-derived furfural hydrogenation is crucial for sustainable chemical production. Herein, we report a systematic study of transition metal catalysts for electrocatalytic furfural reduction to furfuryl alcohol (FA) synthesized by precisely controlled magnetron sputtering. Monometallic thin films (Cu, Ni, Co, Ag, Cr, Mo and W) on Ti substrates reveal a volcano-shaped correlation between the d-band center position and catalytic activity, establishing fundamental binding energy-activity relationships. Building on these insights, we designed bimetallic CuNi alloys with tunable compositions, where the Cu 40 Ni 60 variant demonstrated exceptional performance, achieving twice the FA formation rate of pure Ni while maintaining 100% selectivity. Mechanistic studies reveal that the Cu 40 Ni 60 catalyst exhibits intermediate behavior between Cu (preferring the Langmuir–Hinshelwood pathway) and Ni (favoring the proton-coupled electron transfer pathway), with enhanced contributions from both pathways synergistically boosting the overall reaction rate. Alloying induces synergistic electronic effects that optimize furfural and H adsorption energy to regulate surface coverage and balance the reaction pathways. This work establishes a standardized platform for evaluating composition-activity relationships in furfural hydrogenation and provides fundamental design principles for non-precious metal alloy catalysts, highlighting electronic structure engineering as a key strategy for optimizing hydrogenation performance.
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DOI
PubMed
高影响因子
GREEN CHEMISTRY
·
2021
·Vol. 24
·期 1
·271-284
·
IF 10.182
Xiuzheng Zhuang,Jianguo Liu,Shurong Zhong,Longlong Ma
Amines with functional groups are widely used in the manufacture of pharmaceuticals, agricultural chemicals, and polymers but most of them are still prepared through petrochemical routes. The sustainable production of amines from renewable resources, such as biomass, is thus necessary. For this reason, we developed an eco-friendly, simplified, and highly effective procedure for the preparation of a non-toxic heterogeneous catalyst based on earth-abundant metals, whose catalytic activity on the reductive amination of furfural or other derivatives (more than 24 examples) proved to be broadly available. More surprisingly, the cobalt-supported catalyst was found to be magnetically recoverable and reusable up to eight times with an excellent catalytic activity; on the other hand, the gram-scale tests catalyzed by the same catalyst exhibited the similar yield of the target products in comparison to its smaller scale, which was comparable to the commercial noble-based catalysts. Further results from a series of analytical technologies involving XRD, XPS, TEM/mapping, and in situ FTIR revealed that the structural features of the catalyst are closely in relation to its catalytic mechanisms. In simple terms, the outer graphitic shell is activated by the electronic interaction as well as the induced charge redistribution, enabling the easy substitution of the –NH2 moiety toward functionalized and structurally diverse molecules, even under very mild industrially viable and scalable conditions. Overall, this newly developed catalyst introduces the synthesis of amines from biomass-derived platforms with satisfactory selectivity and carbon balance, providing cost-effective and sustainable access to the wide applications of reductive amination.
研究领域:
催化
·
化学工程
·
材料科学
·
可持续化学
·
纳米技术
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DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2022
·
IF 7.392
Zhengliang Zhang,Zhiwei Zhang,Xubin Zhang,Fumin Wang,Zheng Wang,Yongwang Li,Xingtao Wang,Rosine Ahishakiye,Xu Zhang
Exploring low-cost green catalysts to achieve green organic chemicals and fuels from biomass is one of the crucial ways to solve the energy crisis. The 20 wt% Co-CoO x /AC catalysts were prepared to achieve the one-pot conversion of furfural to 2-methylfuran under milder reaction conditions (120 °C, 2.5 MPa H 2 ), shorter reaction time (5 h) and less catalyst dosage by regulating the ratio of metal to oxide species. The yield of 2-methylfuran reached 87.4 % is achieved under 20 wt% Co-CoO x /AC catalyst conditions, and there was no significant degradation of all catalyst properties after five cycles. Characterization results showed that the active components in the catalyst were present as Co 0 species with CoO x species. The reaction mechanism was explained by combining the characterization results, experimental data and DFT calculations. The formyl group of the furfural side chain is first adsorbed on the Co 0 species, and furfuryl alcohol is produced in the presence of the Co 0 species. Subsequently, the CoO x species adsorbs the C O bond on the side chain, which is broken in the presence of the CoO x species to form 2-methylfuran. The excellent catalytic activity of the 20 wt% Co-CoO x /AC catalyst provide a promising application for preparing 2-methylfuran by hydrodeoxygenation of furfural.
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产品关联
DOI
高影响因子
BIOMASS & BIOENERGY
·
2022
·
IF 5.774
Bang Yao,Qinhao Kang,Jie Fu,Yang Liu,Wenya Ao,Long Wang,Zhihui Jiang,Tianhao Zhang,Yongmeng Song,Zeyu Deng,Asif Ali Siyal,Jianjun Dai
Experiments were carried out to investigate cellulose and furfural from catalytic hydrolysis of corncob. This process improved the comprehensive utilization of hemicellulose and cellulose in biomass resources. Influence of factors (temperature, reaction time, concentration of catalysts, liquid to solid ratio (LSR)) on hydrothermal characteristics, furfural yield, properties and retention of cellulose were investigated through orthogonal and parameter tests. Acetic acid (6 wt%) and FeCl 3 (40 mM) achieved the highest furfural yield (47.60%) and relatively high cellulose retention ratio (71.84%) at 180 °C, 45 min, and 3 mL/g of LSR. While AlCl 3 and citric acid obtained low furfural yield and the lowest cellulose retention ratio (8.38%). Furfural was dominant in distillated organics (GC-MS areas ≥97.9%), by contrast furfural, 5-hydroxymethyfurfural and vanillin were main organics in residual liquors. The peak of furfural yield switched to shorter reaction time as temperature increased. Combination of AlCl 3 with acetic acid and citric acid accelerated cellulose degradation. NaCl inhibited furfural yield and promoted lignin decomposition. Higher temperature and greater concentration of FeCl 3 contributed to reduced crystallinity of cellulose during hydrothermal treatment.
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DOI
高影响因子
BIOMASS & BIOENERGY
·
2023
·
IF 6
Jirui Yang,Yanwei Zhang,Feng Shen,Xinhua Qi
Meerwein-Ponndorf-Verley (MPV) reaction has been widely acknowledged to be a mild catalytic transfer hydrogenation method for selective reduction of biomass-derived furfural to furfuryl alcohol . Herein zirconium-containing mesoporous composite catalyst was developed through the combination of sol-gel process and soft templating method, in which naturally abundant glucose and F127 triblock copolymer were used as the ligand and pore-forming agent, respectively. The hydroxyl groups in glucose molecules were demonstrated to be coordinated with zirconium ion during hydrolysis-condensation of zirconium precursor, leading to the even dispersion of zirconia nanoparticles in the composite catalyst. The composite catalyst was proven to be highly efficient for catalyzing MPV reduction of furfural with the maximum furfuryl alcohol yield of 93.4% at 180 °C within 180 min in 2-propanol, which served as both solvent and reductant . The composite also showed a good reusability . After five consecutive reaction cycles, furfuryl alcohol yield was slightly reduced from 93.4% to 77.7%, but it could be recovered to 92.8% after the reused composite was regenerated with dilute alkali solution. Batch experiments and systematic characterizations demonstrated that the excellent catalytic performance of composite catalyst was determined by multiple factors mainly including the stronger Lewis acidity, a considerable amount of basic site and the rich mesoporous structure. This study provides a facile strategy to prepare multifunctional composite catalysts using naturally abundant carbohydrates as the feedstocks for lignocellulosic biorefinery .
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DOI
高影响因子
RENEWABLE ENERGY
·
2023
·
IF 8.7
Feiyi Chen,Yue Wang,Junhua Zhang,Huai Liu,Lincai Peng
Although metal oxide has unique advantages in catalytic transfer hydrogenation (CTH) of furfural (FAL) into furfuryl alcohol (FOL), the excessive stability of the metal site and oxygen coordination leads to the inert Lewis acid site in the oxide, which affects the catalytic activity and limits its broader application. It is known that the hydroxyl group on the oxide surface can promote the adsorption of isopropanol in an alkoxide species by assisting its deprotonation, thereby activating the metal site and enhance the overall reaction activity. However, constructing metal oxide with rich hydroxyl groups is always challenging. This contribution prepared a series of HfO 2 nanoparticles (NPs) with rich hydroxyl groups through hydrothermal methods . Systematic characterizations proved the presence of hydroxyl groups on the surface of HfO 2 NPs, which promoted its adsorption capacity for isopropanol (hydrogen donor and reaction solvent) and substrate (FAL), thus accelerating the subsequent reaction for CTH of FAL into FOL. As a result, a 100% of FAL conversion with 95.2% of FOL yield was obtained at 160 °C in 4 h, which has significant advantages over commercial and other literature reported oxides. This finding provides a new idea for designing of efficient metal oxides for the CTH reaction by enhancing the hydroxyl group.
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DOI
高影响因子
ACS Catalysis
·
2023
·
IF 12.9
Wei Lin,Yi Chen,Yuexing Zhang,Yongsheng Zhang,Jianshe Wang,Liucheng Wang,Chunbao Charles Xu,Renfeng Nie
Ni–ReOx bimetallic catalysts (Ni–ReOx/TiO2) were prepared through a successive impregnation method, which is extremely active in furfural (FAL) hydrogenation to tetrahydrofurfuryl alcohol (THFOL) under mild reaction conditions. For instance, high FAL initial reaction rate (439.4 mmol/g-Ni/h) and THFOL formation rate (80.4 mmol/g-Ni/h) were achieved over Ni–5ReOx/TiO2, which are 13.2 and 6.6 times higher than those of Ni/TiO2, respectively. The unique catalyst reactivity derives from rich Lewis acidic ReOx and intimate electron interaction of ReOx with Ni NPs. Kinetic studies reveal that ReOx decoration decreases the activation barrier of −C═O hydrogenation other than the furan ring. Mechanism studies show that ReOx has a good affinity for C═O and H2 and favors hydrogen spillover and C═O bond activation on Ni, thus reinforcing the synergistic effect of Ni and ReOx. This catalyst is versatile for various furan aldehydes and is relatively stable for 5 times recycling, showing relative potential for industrial application.
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Wei Lin,Yuexing Zhang,Zixu Ma,Zhiwei Sun,Xiaolong Liu,Chunbao Charles Xu,Renfeng Nie
Selectivity controlling is a crucial and challenging issue for the hydrogenation of furfural (FAL) to cyclopentanone (CPO). Herein, Ni 3 Sn 2 -ReO x /TiO 2 is synthesized via successive impregnation and exhibits full conversion and 92.5 % CPO selectivity under 3.0 MPa H 2 at 140 °C, which are much higher than those of Ni/TiO 2 and Ni 3 Sn 2 /TiO 2 . Characterizations show that Ni 3 Sn 2 is the main active phase that remarkably restrains the over-hydrogenation of the furan ring, while ReO x plays an electrophile or Lewis acid site to activate C-OH of furfuryl alcohol and induces its rearrangement. DFT calculations verify that Sn doping weakens the furan ring adsorption on Ni 3 Sn 2 and shifts its adsorption configuration, which consequently inhibits side reactions and favors the metal-acid (Ni 3 Sn 2 -ReO x ) synergy. The catalyst is stable, recyclable and also active at even 0.5 MPa H 2 and 80 °C. This study provides an advanced strategy for the rational design of superior catalysts for tuning product selectivity, with practical potential for upgrading biomass-derived platform molecules.
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DOI
高影响因子
Reaction Chemistry & Engineering
·
2023
·Vol. 8
·期 11
·2796-2803
·
IF 3.9
Liangli Li,Mingzhu Yang,Long Cheng,Jingjing Shi,Jinsheng Gou,Junming Xu
Electrocatalytic hydrogenation (ECH) proved to be a highly efficient and eco-friendly approach for transforming biomass derivatives into valuable chemicals and biofuels, although in most cases, the reaction time was lengthy. In this study, a carbon loaded Pt–Co bimetallic catalyst (PtCo/C) was prepared using a simple chemical reduction method. For the ECH of furfural (FF) to furfural alcohol (FAL), as a platform molecular reaction derived from biomass, the dual catalyst system composed of H3O40PW12 (PW12) showed excellent FF conversion rate (96.7% FF conversion rate achieved in 20 minutes) and FAL selectivity (93.1%). The PtCo/C catalyst was found to possess abundant hydrogen adsorption sites (Hads), resulting in improved electrocatalytic hydrogenation and reduced electrocondensation during fluidization. Simultaneously, the occurrence of the hydrogen evolution reaction as an ancillary process was effectively inhibited at comparatively lower potentials. These discoveries offered significant groundwork and a point of reference for the catalyst advancement and the electrocatalytic conversion of biomass.
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DOI
高影响因子
Molecular Catalysis
·
2023
·
IF 4.6
Fukun Li,Ronghe Yang,Ziting Du,Jinhang Dai,Xingmin Wang,Ning Li,Xianming Zhang,Yunqi Liu,Haifeng Gong,Zhenping Cai,Junjun Shi
Biochemicals and biofuel derived from biomass conversion have received much attention over past decades. Alkyl levulinates are considered as promising building block chemicals and green fuel additive. This work presents a facile and efficient catalytic strategy for one pot cascade conversion of furfural to alkyl levulinates over rare earth metal trifluoromethanesulfonates (RE(OTf) 3 ) in alcohol without external H 2 . Experimental results demonstrate that RE(OTf) 3 binds to the alcohol ((OTf) 3 -RE-O(H)R), possessing both Brønsted acid and Lewis acid, plays a key role for this cascade process. Meanwhile, the selectivity of alkyl levulinate is closely related to charge density of selected metal ion and the reduction potential of the selected alcohol. Among various tests, Lu(OTf) 3 , possessing the greatest charge density, exhibits the best catalytic activity in the lowest reduction potential of 2-propanol. 100% furfural conversion and 52.8% ispropanyl levulinate yield can be achieved at 190°C within 45 min. This catalyst can be recycled five times by direct vacuum distillation and regenerated by oxidative elimination of formed humins. Besides, a plausible reaction mechanism is also proposed.
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DOI
高影响因子
RENEWABLE ENERGY
·
2022
·
IF 8.634
Yiwei Tang,Xiaoning Liu,Ran Xi,Le Liu,Xinhua Qi
As one of the important chemical feedstocks and biofuels, ethyl levulinate (EL) can be produced from biomass-derived furfural by consecutive hydrogenation, etherification and ring-opening reactions. However, this process normally requires two separate steps in different reaction systems, which is complex and energy consumption. Herein, Nb–Ni bifunctional ordered mesoporous carbons (Nb/ [email protected] ) were synthesized by a two-step process where [email protected] was firstly synthesized by a solvent evaporation induced self-assembly (EISA) process using F127 as a template agent, polyphenol gallic acid as carbon precursor and Ni 2+ as cross-linker, following with the supporting of Nb species in the [email protected] by an incipient wetness impregnation method. The as-synthesized Nb/ [email protected] samples were applied for the one-pot catalytic transformation of furfural to EL, and exhibited good activity with the highest EL yield of 83% under an optimized condition. Two possible pathways for the one-pot production of EL were proposed according to two intermediates: (1) hydrogenation of furfural to form furfuryl alcohol (FFA) that is then etherified with ethanol to form 2-(ethoxymethyl)furan (2-EMF); and (2) acetalization and etherification of furfural with ethanol to produce 2-(diethoxymethyl)furan (2-DMF). Then both 2-DMF and 2-EMF are converted to EL through acid catalyzed ring opening reaction. The dominant reaction pathway varied with the properties of the catalyst and the applied reaction conditions.
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DOI
高影响因子
危险品化学品经营许可证（带存储）