Biomass Conversion and Biorefinery
·
2022
·
IF 4.05
Gao De,Han Feng,Waterhouse Geoffrey I. N.,Li Yan,Zhang Lili
A series of FeTPP-N/C-X catalysts were successfully prepared by adsorption of Fe tetraphenylporphine (FeTPP) onto a porous nitrogen-doped carbon (N/C) support using an ultrasonication method. The FeTPP-N/C catalysts were then used for the preparation of 5-hydroxymethyl-2-furan acid (HMFCA) by catalytic oxidation of 5-hydroxymethylfurfural (HMF) at 80 °C. The effects of reaction temperature, NaOH dosage, reaction time, and oxygen pressure on HMF conversion and HMFCA yield were systematically investigated. Under optimized testing conditions, a FeTPP-N/C-1 catalyst prepared using equal masses of FeTPP and N/C delivered a HMF conversion in water of 92.4%, with a selectivity to HMFCA of 97.2% over 6 h at an oxygen pressure of 1.0 MPa. Further, the catalyst showed good stability in five consecutive HMF oxidation tests. Based on the catalytic tests, and detailed catalyst characterization studies before and after reaction, a probable reaction mechanism was proposed for the selective oxidation of HMF to HMFCA by the FeTPP-N/C catalysts. Graphical Abstract
A series of FeTPP-N/C
catalysts were successfully prepared by the adsorption of iron
tetraphenylporphine (FeTPP) onto a porous nitrogen-doped carbon (N/C) support
using an ultrasonication method. The FeTPP-N/C catalysts were then used for the
catalytic aerobic oxidation of HMF to HMFCA. Under the optimized reaction conditions (temperature
80 °C, reaction time 6 h, O 2 pressure 1 MPa), a high HMF conversion
of 92.4% and a remarkable HMFCA selectivity of 97.2% were obtained, suggesting
that the developed noble-metal free catalyst has excellent promise for the
synthesis of valuable HMFCA from HMF.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Ming-Kun Ke,Yuan Min,Shu-Chuan Mei,Hou-Wei Zeng,Zhao-Hua Wang,Tian-Wei Hua,Jie-Jie Chen,Gui-Xiang Huang,Han-Qing Yu
5-Hydroxymethyl-2-furancarboxylic acid (HMFCA) is an important feedstock in chemical and pharmaceutical industries . Its production through aerobic conversion of 5-hydroxymethylfurfural (5-HMF) has promising prospects but is challenged by the over-oxidation. In this work, we develop a refined Pt-Ag co-catalytic strategy to tailor the selectivity of 5-HMF’s aerobic oxidation. By simple in situ addition of AgNO 3 to the thermal catalytic system of Pt nanoparticles , the main products of 5-HMF oxidation could be shifted from 2,5-furandicarboxylic acid (FDCA) to HMFCA with an ultrahigh selectivity of over 99 %. Density functional theory calculations demonstrate that such strategy could alter the HMFCA adsorption sites from Pt to Ag sites and prevent the oxidation of hydroxymethyl group . In addition, this strategy can be extended to other Ag species, such as AgCl, Ag 2 O and AgO. This work provides insights into the Pt-Ag synergistic catalysis and opens up a simple avenue to control the product selectivity for biomass refinement.
研究领域:
催化
·
化学工程
·
材料科学
·
计算化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2019
·
IF 6.97
Jiahuan An,Guohan Sun,Haian Xia
An efficient method for the catalytic aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) was developed using size-controlled Ag nanoparticles (NPs) in an aqueous solution. A series of AgNPs catalysts stabilized by poly(vinylpyrrolidone) (PVP) supported on ZrO2with different Ag loadings were prepared. XRD, TEM, XPS, and FT-IR techniques were used to characterize the nature of these catalysts. The impact of the Ag loading, the molar ratio of PVP to Ag, the reaction temperature and time, and the base type on the conversion of HMF and yield of HMFCA was investigated. The reaction results show that Ag–PVP/ZrO2 catalysts with a bigger particle size (>10 nm) exhibited superior catalytic activity and HMFCA selectivity compared to Ag/ZrO2 with a smaller particle size (ca. 8.5 nm), indicating that the addition of PVP has a promoting effect on the aerobic oxidation of HMF into HMFCA. The 2.5%Ag–PVP/ZrO2(1:1) catalyst presents an excellent activity with 100% conversion of HMF and 98.2% yield of HMFCA in oxygen flow at 20 °C for 2 h.The basicity is also very critical to obtain a high HMFCA yield, especially for the use of high concentration of HMF; i.e., Ca(OH)2 afforded a higher selectivity toward HMFCA compared to the use of NaOH or Na2CO3 under an identical reaction condition. It is revealed for the first time that the presence of a capping agent (PVP) can effectively modulate the metal–support interaction. Interestingly, it is found that the relatively weak interaction between Ag NPs and the ZrO2 support has a beneficial effect on the conversion of HMF. This work provides new insights into the relationship between the metal–support interaction mediated by PVP molecule and the activity and selectivity of the oxidation reaction.
研究领域:
催化化学
·
材料科学
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
ChemCatChem
·
2025
·
IF 3.9
Zhi Cao,Haitao Cao,Chao Liu,Zhongxiang Fan,Yixiang Shi,Yin Wang,Tao Shen,Lei Li,Gang Qi
Here, a series of schiff-base porous organic polymer-supported silver-nanoparticle, Ag0 NPs@PPTA-x were prepared with a two-step ion coordination/hydrogen reduction. The resulting composite Ag0 NPs@PPTA-9.08 shows excellent catalytic performance for HMF oxidation to HMFCA, and an impressive HMFCA yield of 99.3% was achieved under optimal condition (NaOH 1.5 eq, 50 mL/min air flow, 20 °C, 6 h). Analysis techniques such as ICP-OES, XRD, TEM, SEM, N2 adsorption-desorption, and XPS were employed to characterize the structure and properties of Ag0 NPs@PPTA-x. The results indicate that the coordination of the nitrogen atom is the key factor for the higher activity and stability of Ag0 NPs@PPTA-9.08. The results of leaching and reusing tests as well as structural characterization (XRD, SEM, and FT-IR) shows that the Ag0 NPs@PPTA-9.08 has good stability and robustness structure. Furthermore, a gram-scale oxidation of HMF indicates this catalytic system can be readily scaled up to an industrial level. Finally, the results of other aldehydes oxidation over Ag0 NPs@PPTA-9.08 indicate the good substrate adaptability of the Ag0 NPs@PPTA-9.08. This work provides a new method for stabilizing nano-silver catalysts and opens up a simple avenue to selective oxidation of aldehydes that easily to scaled up.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2019
·
IF 5.162
Mao Wen,Xue-Ying Zhang,Min-Hua Zong,Ning Li
Furan carboxylic acids are important building blocks in polymer and fine chemical industries. In this work, a simple substrate adaptation strategy was applied to improve the catalytic performances of Comamonas testosteroni SC1588 cells for the synthesis of various furan carboxylic acids. It was found that biocatalytic synthesis of 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) was substantially promoted by adding histidine and increasing cell concentrations. HMFCA was produced in a quantitative yield from 200 mM HMF in 24 h. Besides, the HMFCA yields of 71%–81% were achieved with the substrate concentrations up to 250–300 mM. It was firstly found that 4-tert-butylcatechol (TBC), as the stabilizer present in HMF, exerted a significantly detrimental effect on whole-cell catalytic synthesis of HMFCA at high substrate concentrations (more than 130 mM). In addition, a variety of furan carboxylic acids such as 2-furoic acid, 5-methyl-2-furancarboxylic acid and 5-methoxymethyl-2-furancarboxylic acid were synthesized with the yields up to 98%.
研究领域:
生物技术
·
化学工程
·
有机化学
✓ 已验证
产品关联
DOI
高影响因子
BIOCHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 3.9
Siyuan Chang,Bingfeng Li,Tianyi Chen,Leilei Zhang,Yaru Li,Xuejun He,Sen Zhang,Xin Pan
The catalytic transformation of biomass-derived 5-hydroxymethylfurfural (HMF) into value-added chemicals and biofuels has received considerable interest. Previously, we demonstrated that Pseudomonas aeruginosa PC-1 could be used for selective 900 mM HMF oxidation into 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) with over 90% yield. Here, we aimed to mine the potential aldehyde dehydrogenases (ALDHs) for HMF biocatalysis and improved the catalytic activity and tolerance through protein engineering. ALDHs were heterologously expressed in E. coli BL21 (DE3) and subsequently the most efficient HMF oxidation conditions of E. coli /pET -PaALDH70140 were identified. Based on the structural analysis of PaALDH70140 with the HMF and NAD + complexes, the engineering hotspots in the active site architecture were identified and subjected to saturation mutagenesis . The mutant L172R displayed 175% higher HMF catalytic efficiency than PaALDH70140, and the mutant also showed improved HMF-tolerance. Kinetic parameters suggested that L172R had higher HMF affinity and catalytic efficiency, indicating a higher HMF conversion efficiency than the wild-type. Molecular docking revealed that the mutation introduced new hydrogen bonds between the enzyme and HMF, which fixed the spatial position of HMF and shortened the reaction time of the catalysis, thus enhancing the catalytic efficiency of HMF. In the fed-batch process, E. coli /pET -PaALDH70140 - L172R exhibited a 166% increase in the yield of HMFCA within 22 h, proving its potential for HMF bioconversion applications.
研究领域:
生物化学
·
生物技术
·
酶工程
·
催化
✓ 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）