FUEL
·
2024
·
IF 6.7
Wenli Zhang,Yijie Zhou,Zhenzhen Wu,Cheng Pan,Qunpeng Cheng,Guozhi Fan
A porous sulfonic acid-functionalized zirconium-based metal–organic framework possessing both Lewis acid and Brønsted acid sites (UiO-66-SO 3 H) was synthesized and tested for the selective conversion of furfural (FUR) to isopropyl levulinate (IPL) through one-pot cascade reaction. UiO-66-SO 3 H exhibited excellent catalytic performance, and the conversion of FUR as well as the yield and selectivity of IPL reached 96.4 %, 86.0 %, and 89.2 %, respectively. UiO-66-SO 3 H could be simply recovered and reused, but the catalytic performance was significantly decreased. The FUR conversion and IPL yield dropped to 73.8 % and 65.1 %, respectively, after 1 cycle, and the reason for the decrease in the catalyst activity were also investigated. It was found that the decrease was mainly caused by the loss of some −SO 3 H groups, and the cyclic performance of UiO-66-SO 3 H could be restored by supplementing a small amount of BDC-SO 3 Na. A plausible mechanism for the selective synthesis of IPL from FUR was proposed, wherein both Lewis acid and Brønsted acid sites played important roles. This work provides guidance for the selective conversion of FUR into IPL, and the high-valued utilization of biomass and its derivatives.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2018
·
IF 3.141
Haijun Guo,Hairong Zhang,Liquan Zhang,Can Wang,Fen Peng,Qianlin Huang,Lian Xiong,Chao Huang,Xinping Ouyang,Xinde Chen,Xueqing Qiu
Acid-activated attapulgite (H+-ATP)-supported NiCoB amorphous alloy catalysts were applied to the selective hydrogenation of furfural (FUR) to furfuryl alcohol (FA). The reduction process between metallic ions impregnated in/on H+-ATP and BH4– is important to modify the textural properties of catalyst, because of the secondary activation of H+-ATP. The enhancement of interaction between H+-ATP and NiCoB particles promotes the dispersion of NiCoB amorphous alloy. Under the optimal conditions (140 °C, 3 MPa H2, 800 rpm, 3.8 wt % of NiCoB active component with respect to FUR), FUR conversion of 91.3%, and FA selectivity of 82.0% were achieved over the best catalyst (20%NiCoB/H+-ATP). Moreover, the catalyst was recycled six times and showed an increase of 3.9% in FUR conversion and 8.2% in FA selectivity, which might be due to the newly generated Co–Ni alloy active site. The low-cost nature of H+-ATP makes the supported NiCoB catalyst a potential catalyst for the industrial production of FA.
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CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Jiaxin Huang,Chongshuai Gao,Shijun Liu,Xiaorui Du,Wenguang Zhou,Chenguang Wang
Alloying Cu-based catalysts by doping other metals at single atom level is an effective way to improve their hydrogenation performance of biomass-derived molecules. However, the application of Cu-based single atom alloy catalyst in the catalytic hydrogen transfer reaction system remains to be unrevealed. Here, we develop Al 2 O 3 supported CuPd alloy catalysts, among which the single atom alloy catalyst with Pd dispersed in single atomic level on the surface was successfully obtained by controlling the metal amount, such as Cu 8 Pd 1 /Al 2 O 3 with the Cu/Pd Molar ratio of 8: 1. The catalytic performance for furfural hydrodeoxygenation to 2-methylfuran of the CuPd/Al 2 O 3 catalysts, using isopropanol as a hydrogen donor, shows a volcano-type relationship to the Cu/Pd ratio. The highest 2-methylfuran yield (81% at 220 °C) was achieved on the single atom alloy catalyst Cu 8 Pd 1 /Al 2 O 3 . The underlying reaction mechanism of furfural hydrodeoxidation on Cu 8 Pd 1 /Al 2 O 3 was revealed by a series of isotopic labeling experiments, that the furfural was firstly hydrogenated to be furfuralcohol by a metal site-mediated catalytic transfer hydrogenation pathway, and then the furfuralcohol was converted to be 2-methylfuran by a Lewis acid-mediated furan ring activation route. The weak Lewis acid site that formed by single atom Pd alloyed with CuO matrix on Cu 8 Pd 1 /Al 2 O 3 was proposed as the active site for the highly selective generation of 2-methylfuran.
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Molecular Catalysis
·
2024
·
IF 3.9
Siyi Pu,Lu Sun,Chunyan Yang,Jie Chu,Ying Wang,Chungang Min,Xiaoqin Zou,Changfu Zhuang
The low-cost Cu-based catalysts have excellent selectivity in biomass hydrogenation, but it is challenging to improve their catalytic activity at low temperature. Herein, the trimetallic Cu x CoZn@NC (where x = 0.1, 0.3, 0.5 mmol is the molar mass of Cu) were prepared by in suit pyrolysis using trimesic acid with stronger coordination ability. When it was applied to the furfural (FF) selective hydrogenation process, the catalytic yield of the optimal Cu 0.3 CoZn@NC reached >99 % under mild condition of 90 °C, which was 29 times superior to that of the CoZn@NC without Cu doping. The results demonstrate that the doping of Cu reduces the activation energy of Cu x CoZn@NC and increases the catalytic activity at low temperature relative to CoZn@NC. The characterizations and density functional theory (DFT) calculations show that the incorporation of suitable Cu content enhances the interaction between Cu and Co. The amount of surface-active Co 0 and the electron density are significantly enhanced, which effectively stimulates the dissociation of hydrogen. Moreover, the Lewis acid content is significantly increased to facilitate the adsorption and activation of FF. Meanwhile, the impact of Cu content variation on the performance of the multi-metal catalyst is discussed. This work is promising to establish a foundation for the accurate design of polymetallic catalysts through adjusting the Cu content to regulate the reaction activity and selectivity.
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CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Wei Luo,Song Song,Wuyu Zhao,Tong Ding,Ye Tian,Xingang Li
Bimetallic catalysts are promising materials for high-efficient conversion of lignocellulose to value-added chemicals, but synthetic methods with reasonable generality are still lacking. Herein, we report a novel method for synthesizing bimetallic catalyst PtCu@S-1(S-1, silicalite‑1) via zeolite encapsulation with the aid of protecting chelating ligands. PtCu@S-1 displays remarkable activity for the hydrogenation of furfural (FUR) to furfuryl alcohol (FOL), and its apparent turnover frequency (TOF) values reach up to 735 mmol FUR ·mmol Pt −1 ·h −1 and 88 mmol FUR ·mmol Cu −1 ·h −1 , which are ∼ 16 and ∼ 4 times higher than that of Pt@S-1 and Cu@S-1. Interestingly, we for the first time find that OO-trans FUR is a preferable adsorption configuration over OO-cis FUR on PtCu@S-1 due to the Pt sites coordinating with the carbon atom on the furan ring. More importantly, the adsorption ability of OO-trans FUR is stronger than that of OO-cis FUR, which increases the concentration of adsorbed species on PtCu@S-1 and accelerates the hydrogenation of FUR.
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CATALYSIS LETTERS
·
2025
·Vol. 155
·期 4
·1-8
·
IF 2.4
Zhang Qian,Li Yuanzheng,Pan Zhengyi,Wang Guang-Hui
Catalytic transfer hydrogenation (CTH) of α , β -unsaturated aldehydes to α , β -unsaturated alcohols over metal oxide catalysts is of potential for industrial application. Herein, we have developed a Ni/f - Al 2 O 3 catalyst comprising atomically dispersed Ni δ + (2 < δ < 3) species on porous leaf-like Al 2 O 3 , over which a > 97% yield of furfuryl alcohol (FOL) from CTH of furfural (FFR) is obtained with a turnover frequency (TOF) of 216 h − 1 . Most importantly, the catalyst can be recycled at least 6 times without obvious loss of activity. Its superior catalytic performance can be attributed to the abundant and stable Ni δ + -type acid-base pairs on the surface of Ni/f - Al 2 O 3 .
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FUEL
·
2024
·
IF 6.7
Yilin Wei,Zhiwei Sun,Qingqing Li,Dan Wu,Jianshe Wang,Yuexing Zhang,Chunbao Charles Xu,Renfeng Nie
Cost-effective and environmentally friendly production of biomass-derived amines under mild conditions is highly desirable but challenging. Herein, bifunctional Co@CoO x catalysts comprised of Co and CoO x were prepared by controllable precipitation-reduction and adopted for furfural (FAL) reductive amination with N 2 H 4 . The structure of Co species can be regulated gradually via tuning reduction temperature, resulting in a significant influence on reductive amination. The optimal CoO x -250 can achieve 96.4 % furfurylamine (FFA) yield at 60 °C, and even 95.8 % at 30 °C. The control experiments and DFT calculations suggest that the metal Co is responsible for H 2 dissociation and C N reduction, while the oxygen-vacant CoO x favors the hydrogen spillover and the C N bond activation, thus resulting in a collaborative effort for FAL reductive amination. The catalyst is stable and versatile for various aldehydes/ketones with amine yields around 95–99 %, showing great potential for industrial application.
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CHEMICAL ENGINEERING JOURNAL
·
2017
·
IF 6.216
Kaijun Dong,Jun Zhang,Weimin Luo,Lin Su,Zhilin Huang
An acid functionalized porous organic hyper-cross-linked polymer (HCP) derived from benzene monomer was prepared for catalytic dehydration of carbohydrates into 5-hydroxymethyl furfural (HMF) in a DMSO solvent. Systematic characterizations of the HCP catalysts including essential structural properties, sulfur content and acid amount, were identified by XRD, XPS, FESEM, Raman, NH 3 -TPD, TGA, nitrogen physisorption and elemental analysis. Optimization of reaction parameters such as acid amount, solvent, substrate type, temperature and catalyst dosage, and comparison with reported solid acids were systematically investigated. The results showed that sulfonated HCP materials were highly active in fructose dehydration, which could afford a highest HMF yield of 96.7% at almost 100% fructose conversion in 30 min. Furthermore, the catalyst presented satisfied performance and stability during recycling tests. More importantly, the sulfonated HCP catalysts also exhibited promising activity in hydrolytic reaction, esterification and transesterification for platform chemicals production in biomass transformation.
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JOURNAL OF THE CHINESE CHEMICAL SOCIETY
·
2017
·Vol. 64
·期 7
·786-794
·
IF 0.935
Yi Huang,Chunyan Wu,Wenwen Yuan,Yongmei Xia,Xiang Liu,Huamei Yang,Haijun Wang
Catalytic oxidation of renewable furfural into valuable maleic acid in aqueous solutions using metalloporphyrin catalysts was investigated for the first time. The synthesized catalysts were characterized by FT-IR, UV–vis, 1 H NMR, elemental analysis, and TGA. The catalysts varied in metal active sites and functional groups, which had different effects on their catalytic activity. Furthermore, the effects of temperatures, reaction time, catalyst loading, and oxygen pressure were studied in detail. Maleic acid could be achieved in 44% yield by using FeT(p-Cl)PPCl as catalyst under optimal conditions. Finally, FeT(p-Cl)PPCl could be reused in five consecutive runs without a significant loss of activity.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Yongjia Liang,Jianliang Zuo,Zhaohao Cai,Weican Huang,Jing Lin,Zili Liu
The ability to effectively control furan ring opening is the key to transforming furfural into 1,5-pentanediol. Herein, a series of Co-based catalysts modified with rare-earth metals (Y, Pr, La, and Ce) were synthesized. It was found that Y-modified Co-based catalyst with a Co/Y molar ratio of 3.5/0.5 exhibited the highest selectivity for 1,5-pentanediol (53.7%) at 150 °C and 4 MPa H2 in isopropanol (time = 5 h). Coordination between Co and Y in the catalyst resulted in more CoOx and oxygen vacancies, which are vital factors for cleaving the C–O bond of the furan ring. In addition, highly dispersed small-sized Co0 particles on the catalyst surface could boost the dissociation of H2 molecules, which attacked the carbonyl group in the furan ring of furfural to afford 1,5-pentanediol. Density functional theory calculations revealed that the presence of CoOx/Y2O3 oxide interfaces promoted adsorption of furfural (especially via the furan ring) and hydrogenolysis during the hydrogenation process. Modifying a Co-based catalyst with rare-earth metals offers a novel approach for producing 1,5-pentanediol from furfural.
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Materials Today Communications
·
2024
·
IF 3.7
Cheng Chen,Jingbao Zhang,Lihua Zhu,Yu Fang,Jinhui Li,Huan Zhang
The Ru/WO 3 catalysts with various Ru contents (Ru weight percent-0.47 %, 0.96 %, 1.91 %, denoted as Ru/WO 3 -1, 2, 3, respectively) are prepared through NaBH 4 liquid phase chemical reduction strategy. Ru is uniformly dispersed as nanoparticles and nanoclusters on the WO 3 nanorods, and the catalytic performance of the Ru/WO 3 -3 catalysts for furfural (FF) selective hydrogenation at relatively mild conditions (reaction temperature-60 ℃, reaction time-8 h, hydrogen pressure-2.0 MPa) is investigated. It is found that the Ru/WO 3 -3 catalyst exhibits the most excellent catalytic performance, with 85.2 % conversion of FF, 97.3 % selectivity of furfuryl alcohol (FA), and highly stable. Characterization of XRD, XPS, TEM, HRTEM, H 2 -TPD, H 2 -TPR, N 2 -physical adsorption-desorption, STEM-EDX elemental line-scannig and mapping reveal that there is a synergistic effect and strong interaction between Ru and WO 3 . The ruthenium nanoclusters and nanoparticles are beneficial to the activation of H 2 , forming activated hydrogen species (H*), the interface of Ru-O-W is in favor of the adsorption and activation of C O, thus improving the selectivity of C O hydrogenation and forming FA.
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Applications in Energy and Combustion Science
·
2025
·
IF 6
Zhongyue Zhou,Haoran Liu,Xinghua Liu,Chih-Hao Chin
Coke deposition and catalyst deactivation represent significant challenges in catalytic research, yet the mechanisms underlying their formation remain inadequately understood. Herein, we employed the HZSM-5 catalyzed conversion of furfural as a model reaction and, using a newly developed online high-resolution mass spectrometry (HRMS) technique, directly detected a broad spectrum of oxygenated polycyclic aromatic hydrocarbons (OPAHs) under reaction conditions. Solid-state NMR further revealed the functional group architectures of OPAH side chains in condensed-phase coke, while density functional theory (DFT) calculations elucidated plausible formation and transformation pathways. These complementary approaches establish that highly active OPAHs serve as crucial intermediates in the coke deposition process. We propose a novel mechanism in which light OPAHs, orginating from small-molecule products, undergo rapid polymerization at the active sites to yield larger polycyclic aromatic hydrocarbons, traditionally classified as coke. This newly identified mechanism highlights the unexpectedly rapid coking during the catalytic pyrolysis of biomass, and underscores the significant role of OPAHs in catalyst deactivation. By providing molecular-level insights into coke growth, this study lays a foundation for strategies to suppress coke formation, thereby improving the efficiency and sustainability of catalytic conversion technologies for biomass utilization.
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