ChemCatChem
·
2025
·
IF 3.9
Yu Tang,Kaiyang Xu,Lingfeng Weng,Yuanjie Xu,Li Tan,Lizhi Wu
Cyclopentanone (CPO) is a high-value platform chemical widely used in fuel, fragrances, and polymers, yet its sustainable production from biomass remains challenging. This work addresses this gap by developing efficient Ni/TiO 2 catalysts through crystal phase engineering of TiO 2 supports (anatase, rutile, mixed-phase P25) for aqueous-phase hydrogenative ring-rearrangement of furfural (FAL) to CPO. Crucially, the TiO 2 phase dictates the Ni–O–Ti interface structure, governing nickel speciation and reactivity. Ni supported on mixed-phase P25 achieves exceptional performance under industrially relevant conditions: 91.1% FAL conversion, 89.3% CPO selectivity, and specific rate of 71.6 h −1 , surpassing catalysts on pure anatase (9.1% conversion) or rutile (55.8% conversion). Physical mixture experiments confirm this superiority stems from the intrinsic interface of P25, not component blending. Characterization reveals that P25 stabilizes a multifunctional surface ensemble: metallic Ni⁰ (18.0% by XPS) enables hydrogenation, while cationic Ni 2+ facilitates acid-catalyzed dehydration and ring rearrangement. Simultaneously, sufficient metal–support interaction permits in situ regeneration of active sites. The optimized 1Ni/P25 demonstrates robust stability over five cycles with retained selectivity (>90%), showcasing practical durability. This study provides a scalable design strategy—support crystal phase tuning—to engineer cost-effective, multifunctional catalysts for industrial biomass upgrading, advancing green manufacturing of cyclic ketones without precious metals. Graphical This study investigates how the TiO 2 crystal phases (anatase, rutile, and P25) affect Ni-based catalysts in the conversion of furfural (FAL) to cyclopentanone (CPO). Ni/TiO 2 -P25 shows superior performance: 91.1% FAL conversion and 89.3% CPO selectivity, outperforming that on anatase and rutile. It stabilizes mixed-valence Ni (Ni° for hydrogenation, Ni 2+ for acid-catalyzed steps) via unique Ni–O–Ti interfaces, enabling efficient FAL conversion.
✓ 已验证
产品关联
DOI
高影响因子
Processes
·
2026
·Vol. 14
·期 2
·223
·
IF 2.8
Tianran Kong,Annan Zhao,Yinghui Zhang,Zongxuan Bai,Hongying Lü,Kaixuan Yang
Efficient conversion of biomass-based platform molecules into high-value derivatives is recognized as one formidable challenge in biomass upgrading. In this work, a one-pot deep eutectic solvents-assisted solvothermal method was developed for the modification of the commercial Pt/C catalysts by introducing a secondary metal (M = Sn, Bi, Ge, Sb, Pb). The structural and electronic properties of the catalysts were precisely tuned. Among the screened metals, the addition of Sn yielded the most significant improvement in catalytic activity. The optimized PtSn0.5/C-140 catalyst achieved superior furfural (FAL) conversion and furfuryl alcohol (FOL) selectivity under mild conditions (20 °C, 2 MPa H2). Comprehensive characterizations, including XRD, HRTEM, XPS, and H2-TPD, confirmed the formation of Pt-Sn solid-solution phase. Furthermore, Characterization and reaction results revealed that the electronic and geometric effects induced by Sn modulated Pt active sites, significantly enhancing the adsorption of the active H species. Additionally, the SnOxspecies adjacent to the Pt-Sn sites served as hydrogen spillover acceptors, further accelerating the hydrogenation process. The synergy between the Pt-Sn solid-solution phase and SnOxspecies is identified as the origin of the superior performance at room temperature. These findings provide a new strategy for the design of high-performance biomass conversion catalysts by upgrading commercial noble metal catalysts.
✓ 已验证
产品关联
DOI
高影响因子
Nanomaterials
·
2023
·Vol. 13
·期 2
·285
·
IF 5.3
Dandan Liu,Qiuju Fu,Chao Feng,Taisan Xiang,Han Ye,Yuting Shi,Liangjun Li,Pengcheng Dai,Xin Gu,Xuebo Zhao
A rational design of transition metal catalysts to achieve selective hydrogenation of furfural (FFR) to tetrahydrofurfuryl alcohol (THFA) under facile conditions is a promising option. In this work, a series of Ni catalysts were synthesized by controlled thermal treatment of Ni-based metal-organic frameworks (MOFs), with the purpose of modulating the interface of nickel nanoparticles by the reticular coordination in MOF precursors. The catalytic performance indicates that Ni/C catalyst obtained at 400 °C exhibits efficient conversion of FFR (>99%) and high selectivity to THFA (96.1%), under facile conditions (80 °C, 3 MPa H2, 4.0 h). The decomposition of MOF at low temperatures results in highly dispersed Ni0particles and interfacial charge transfer from metal to interstitial carbon atoms induced by coordination in MOF. The electron-deficient Ni species on the Ni surface results in an electropositive surface of Ni nanoparticles in Ni/C-400, which ameliorates furfural adsorption and enhances the hydrogen heterolysis process, finally achieving facile hydrogenation of FFR to THFA.Keywords:Ni catalyst;furfural hydrogenation;tetrahydrofurfuryl alcohol;metal-organic frameworks;interstitial atom
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2023
·
IF 4.2
Rongrong Li,Wenqi Liu,Huibin Liu,Hongyu Niu,Quan Zhou,Changhai Liang,Xiao Chen
One-pot hydrogenation of biomass-derived furfural with multiple reduction sites requires suitable metal sites to achieve a high value-added chemical in high yield. In this work, nonprecious Ni–Fe bimetallic catalysts with high efficiency derived from FexNiy/MgAl-LDH hydrotalcite precursors are prepared for one-pot sequential hydrogenation of furfural to tetrahydrofurfuryl alcohol at mild conditions. Through fine adjustment of metallic Fe/Ni molar ratios in hydrotalcite precursors, bimetallic FexNiy/MgAlO catalysts can be constructed. The topological transformation of hydrotalcite precursors provides a mesoporous structure for bimetallic supported catalysts. Due to the formation of the Ni–Fe alloy, there is an electron transfer from Fe to Ni in the catalyst due to the higher electronegativity of Ni than that of Fe, which greatly influences the adsorption of furfural on the surface of catalysts. Comparing the structures and catalytic performances of monometallic Ni/MgAlO and Fe/MgAlO catalysts, the Ni-rich Fe1Ni4/MgAlO catalyst with the dual active sites of metallic Ni and FeNi3 alloy presents high efficiency in sequential hydrogenation of the C═O bonds and C═C bonds of furfural to tetrahydrofurfuryl alcohol with the yield of 90.3% under 3 MPa H2 and 80 °C for 3 h, which can be an alternative for noble metal catalysts. Additionally, the Ni-rich Fe1Ni4/MgAlO catalyst presents excellent cycling stability. This design strategy for nonprecious NiFe bimetallic catalysts not only provide promising candidates for effective utilization of biobased furfural but also extend the application of bimetallic catalysts derived from hydrotalcite precursors for one-pot hydrogenation reactions.
✓ 已验证
产品关联
DOI
高影响因子
ChemCatChem
·
2022
·Vol. 14
·期 18
·e202200704
·
IF 5.497
Fan Song,Shuangshuang Cen,Cong Wan,Lijun Wang
Graphical This work presented a stable and high-efficient synergistic catalytic system based on Au nanoparticle anchored in organic base group-grafted silica aerogel for oxidative esterification of furfural with H 2 O as a by-product, which has excellent resistance to deactivation induced by product adsorption and leaching of the components, and can almost completely convert furfural to alkyl furoate in 7 cycles. Inorganic metal (hydro)oxide supports with appropriate basicity or acid-base properties can promote oxidative esterification of furfural over Au-based catalysts, however, they suffer the problems of easy inactivation induced by the leaching of the components in this water-producing reaction and the shield of catalytic sites by product adsorption. In this work, we report efficient and stable oxidative esterification of furfural over Au nanoparticles anchored in aminopropyl-grafted silica aerogel. The support is insoluble and possesses no strong Lewis acid sites to adsorb oxygen-containing products or intermediates, reducing the probability of catalyst deactivation induced by adsorption. In 7 cycles of reactions, the catalyst maintained the initial activity without any treatments, the yields of alkyl furoate kept above 98 %, and no agglomeration and leaching of Au occurred. Moreover, the roles of Au, alkyl chain, −NH 2 group and Au-activated O species in reactions were clarified, and accordingly, a possible catalytic mechanism involving oxidative dehydrogenation was given.
✓ 已验证
产品关联
DOI
高影响因子
Scientific Programming
·
2022
·
IF 1.672
Xiaojun Pei,Haojun Shu,Yisi Feng
In the field of catalysis, the support of the catalyst is often composed of hollow carbon materials. In order to monitor the preparation of nitrogen-doped carbon-based bimetallic copper-cobalt catalysis and its hydrogenation reaction in furfural, using m-aminophenol as the nitrogen source, formaldehyde as a carbon source, and P123 as a template agent, a nitrogen-doped bimetallic copper-cobalt mesoporous carbon catalyst Cu-Co@N-MPC-500 was synthesized by the hydrothermal method. The morphology, structure, and chemical composition of the catalyst were analyzed by means of TEM, XRD, BET, and XPS, respectively. The results show that the nitrogen-doped mesoporous carbon has a stable structure, uniform pore size distribution, and the nano-copper-cobalt particles are uniformly dispersed in the mesoporous carbon surface. Through furfural hydrogenation, the catalyst selectivity and cycle stability were discussed. Under the furfural conversion rate of 96.1%, the yield of cyclopentanone could reach 76.2%. After 5 cycles, the catalytic efficiency of the catalyst did not decrease significantly. It shows that Cu-Co@N-MPC-500 has excellent application prospects in the field of industrial production.
✓ 已验证
产品关联
DOI
高影响因子
SENSORS
·
2021
·Vol. 22
·期 1
·64
·
IF 3.576
Yuzhen Li,Juanhua Zhang,Mengxiao Lv,Yihui Bai,Xuexiang Weng,Chunping You,Zhenmin Liu
The concentration of 5-hydroxymethyl-2-furfural (HMF) is an important quality-related index in milk and milk products. Fast, cost-effective and environmentally friendly determination of HMF is of great significance in milk products control. In this study, a three-dimensional (3D) graphene-like surface (3DGrls) was successfully prepared within 5 min by an electrochemical amperometric pretreatment on a pencil graphite electrode (PGE). The fast-obtained 3D graphene-like surface increased the electrode surface area and enhanced the electron transfer capability without the addition of any harmful chemicals. The morphology and chemical composition of the obtained electrode were characterized by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and electrochemical impedance spectroscopy (EIS). The results found that the electrochemical response to HMF at the prepared 3DGrls/PGE was 34 times higher than that at PGE. The modified electrode showed a good linear response to HMF in a concentration range of 0.35~116 μM with a low limit of detection (LOD) of 0.099 μM. The integrated electrode also exhibited excellent stability and wonderful antifouling property. Furthermore, the 3DGrls/PGE was successfully applied for the determination of HMF in three processed cheese samples with satisfactory results.Keywords:5-hydroxymethyl-2-furfural;pencil graphite electrode;three-dimensional graphene-like surface;sensor;processed cheese
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Biomass Conversion and Biorefinery
·
2019
·Vol. 10
·期 4
·795-802
·
IF 2.326
Li Yan,Wu Weibo,Li Hu,Zhao Wenfeng,Yang Song
Furfuryl alcohol (FOL) is one of the versatile molecules in the chemical industry, and can be obtained from the biomass-derived furfural (FAL) via selective hydrogenation. In this study, a mild and rapid protocol was developed for the efficient reduction of FAL to FOL in the presence of an eco-friendly ionic liquid tetrabutylammonium fluoride ([TBA]F) using 1,1,3,3-tetramethyldisiloxane (TMDS) as the hydrogen source. After reacting at room temperature for 5 min, a high FOL yield of 97% with a remarkable TOF value of 310 h −1 could be achieved. The activation of TMDS with fluoride was found to play a key role in the acceleration of the hydrogenation process, and ATR-FTIR and HR-MS were used to verify the possible reaction pathway.
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Yongwang Li,Qi Shen,Yao Nian,Fumin Wang,Xubin Zhang,Zhengliang Zhang,Changhao Bing,Xiaolu Fan,Rosine Ahishakiye
The exploitation of base metal catalysts to upgrade biomass chemicals remains a daunting challenge and a sustainable strategy. Here, a series of Co-Al spinel catalysts are rapidly prepared by low-temperature solution combustion synthesis for hydrogenation of furfural (FF) to 2-methylfuran (2-MF), in which oxygen vacancies are easily manipulated by regulating the proportion of glycine in the ingredients. The screened Co/CoAl 2 O 4 incorporating adequate oxygen vacancies yields 2-MF over 97 % at 150 ℃ for 5 h, rivalling the state-of-the-art catalysts to date. Characterizations and DFT calculations attribute the success to oxygen vacancies, which not only enhance the adsorption of FF by changing the adsorption geometry, but also facilitate the hydrogen spillover from Co to substrate by moving down the d -band center of CoAl 2 O 4 . This study provides a versatile methodology for the efficient and low-temperature preparation of spinel and the construction of defect engineering on catalysts, enlightening the design of phenomenal catalysts.
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2020
·
IF 4.244
Tao Yang,Wenzhi Li,Ajibola T. Ogunbiyi,Shengxin An
A novel solid acid catalyst (SO 3 H-NG-C) was synthesized from biomass-derived glucosamine hydrochloride by carbonization, activation and sulfonation processes. The SO 3 H-NG-C was characterized by SEM, TEM, N 2 adsorption-desorption, elemental analysis, XRD, FTIR, Py-IR and XPS to reveal its physical and chemical properties. The SO 3 H-NG-C was used as a catalyst for converting corn stover into furfural and 5-hydromethylfurfural (5-HMF) via a one-step process. The effects of reaction temperature and time, solvent types, water concentrations, corn stover concentration, catalyst loading and catalyst stability were investigated systematically. 53 % furfural yield and17 % 5-HMF yield were obtained from 200 mg corn stover at 190 °C in 80 min using 100 mg SO 3 H-NG-C in Ƴ-valerolactone (GVL). Moreover, the used catalyst was separated from corn stover residue via sieve, and the catalyst showed reasonable stability for corn stover conversion.
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Min Yuan,Tianchang Liu,Qi Shi,Jinxiang Dong
Efficient separation of furfural from an acid-containing aqueous solution is a critical step in the furfural production process. Zeolitic imidazolate framework (ZIF)-derived porous carbons with acid resistance and tunable surface chemistry/pore structure are promising adsorbents for the separation of organic compounds from acid-containing aqueous solutions. However, little attention has been given to establish the trend of distribution of micropores and mesopores in the chemical activation of ZIF-derived porous carbon, which directly affects the adsorption performance. Herein, we investigated the relationship between the distribution of micropores and mesopores and the N species content/type in the chemical activation of the N-doped ZIF-8-derived porous carbon, and the KOH activation mechanism was proposed. The intermediates K 2 CO 3 /K 2 O reacted with the C species of NC ZIF-8 1000C with a low N content, the CO was formed, and the structural deformation was not substantial, which is beneficial for the construction of abundant and larger micropores (10–20 Å), and a few mesopores (20–30 Å). While the reaction of the intermediate K 2 CO 3 /K 2 O with the higher-reactivity C–N species (pyridine and pyrrolic) of NC ZIF-8 800C with a high N content resulted in the formation of the intermediate product KOCN and decomposition product CO and NO, and the structural deformation was substantial, which led to the formation of abundant and larger mesopores (30–60 Å). Furthermore, the furfural (5.0 wt.%) static adsorption on the designed NC ZIF-8 1000C-700A with the abundant micropores is 1189.8 mg g −1 , and the selectivity of furfural/acetic acid mixture (5.0/2.0 wt.%) is 91.5, which exceeds that of traditional adsorbents.
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2019
·
IF 4.191
Xiaoyun Li,Rui Xu,Qingling Liu,Min Liang,Jiaxin Yang,Shuangchun Lu,Guangbi Li,Lefu Lu,Chuanling Si
A one-step process was proposed for valorization of corn stover into furfural and levulinic acid catalyzed by SAPO-18 zeolites. With the aim to produce furfural and levulinic acid, the Brønsted to Lewis acid site ratios of SAPO-18 were modified. The influence of reaction temperature, time and the ratios of Brønsted to Lewis acid site on the valorization of corn stover were investigated. At the fixed catalyst concentration of 20 g/L, a furfural yield of 95.1% was observed at 205 °C for 40 min using SAPO-18 with Brønsted to Lewis acid site ratio of 0.11, and a levulinic acid yield of 70.2% achieved at 190 °C for 80 min using SAPO-18 with Brønsted to Lewis acid site ratio of 0.17. The Brønsted to Lewis acid site ratios of SAPO-18 were adjusted by altering the framework Si/Al ratio of SAPO-18. The SAPO-18 with lower Brønsted to Lewis acid site ratios showed higher activity for furfural production from corn stover and that with higher ratios exhibit superior catalytic effect for levulinic acid formation. The kinetic models considering the effect of Brønsted to Lewis acid site ratios agreed with the experiment values well, which provided detailed insights on the conversion of hemicellulose and cellulose fraction of corn stover into furfural and levulinic acid.
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）