PHYSICAL CHEMISTRY CHEMICAL PHYSICS
·
2018
·Vol. 20
·期 10
·7351-7360
·
IF 3.906
Shan Jin,Yongjun Hu,Pengchao Wang,Huaqi Zhan,Qiao Lu,Fuyi Liu,Liusi Sheng
Water molecules, which serve as both hydrogen bond donors and acceptors, have been found to influence the conformational landscape of gas-phase phenyl-β-D-glucopyranoside. Herein, tetrahydrofurfuryl alcohol (THFA), a sugar-like molecule without chromophores (e.g. phenyl-substitution), was used as the model sugar molecule for exploring the behaviour of water molecules on the conformational landscape of a pentose sugar such as deoxyribose. We used mass selected infrared-vacuum ultraviolet (IR-VUV) (118 nm) spectroscopy to investigate the hydrated neutral THFA and its complex cation in a supersonic jet. High level density functional theory (DFT) calculations were performed to ascertain the experimental results. The results revealed that the water molecule tends to insert into the twisted conformer at a position where two stronger intermolecular hydrogen bonds were formed by breaking the weak intramolecular interactions. We found that the twisted conformer of the hydrated neutral THFA complex is more stable than the envelope conformation, while the latter is more stable for the THFA molecule. However, the conformational landscape of the hydrated THFA complex cation did not significantly change on microsolvation with water molecules. These results indicated that the dominant structural landscape of the hydrated cationic complex is the twisted configuration with a trans-hydroxymethyl group. This finding provides valuable insight into the microsolvation of gas-phase sugar molecules.
研究领域:
化学
·
分子生物学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
FUEL
·
2024
·
IF 6.7
Jun Zhang,Yaoxin Xiao,Rui Shan,Haoran Yuan,Yong Chen
In the present research, calcium decorated copper@nitrogen-doped carbon (marked as Cu 1 Ca x @CN) derived from biomass was constructed for highly selective hydrogenation of bio-based furfural (FFR), which remarkably favored furan ring hydrogenation for tetrahydrofurfuryl alcohol (THFA) formation via regulating the hydrogenation path. Remarkably, the in-situ generated basic sites from N- and Ca-containing species were beneficial to the good metal dispersion as well as the chemical activation of aldehyde and C=C groups, thus favoring the FFR-to-THFA transformation. The optimal basic density-to-copper mass ratio in a range of 3.0 ∼ 4.0 was attained, in consideration of THFA generation. The as-prepared Cu 1 Ca 0.87 @CN catalyst could afford full FFR conversion as well as 75.6 % THFA yield under 3 MPa H 2 atmosphere, which also exhibited excellent stability and could be recycled four times without any deactivation. In addition, the basic sites in the as-prepared Cu 1 Ca x @CN samples were capable of activating both the C=O and C=C bonds, and the activation of C=O bond took precedence over that of C=C bond, especially in the case of relative low temperatures. Plausible reaction mechanism for FFR-to-THFA transformation under the synergistic effect of active Cu 0 center and basic sites was proposed in detail.
研究领域:
催化化学
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生物质能
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Nanomaterials
·
2019
·Vol. 9
·期 12
·1698
·
IF 4.034
Yanliang Yang,Dongsheng Deng,Dong Sui,Yanfu Xie,Dongmi Li,Ying Duan
The hydrogenation of furan ring in the biomass-derived furans is of great importance for the conversion of biomass to valuable chemicals. Fabrication of high activity and selectivity catalyst for this hydrogenation under mild conditions was one of the focuses of this research. In this manuscript, UiO-66-v, in which vinyl bonded to the benzene ring, was first prepared. Then, the uniformly distributed vinyl was used as the reductant for the preparation of Pd/UiO-66-v. The catalyst was characterized by X-ray diffraction, thermogravimetric, N2physical adsorption/desorption, X-ray photoelectron spectroscopy, scanning electron microscope, transmission electron microscopy, energy dispersive spectrometer elemental mappings, and inductively coupled plasma atomic emission spectroscopy to find the Pd/UiO-66-v had a narrow palladium nanoparticles size of 3–5 nm and maintained the structure and thermal stability of UiO-66-v. The Pd/UiO-66-v was used for the hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol in water. 99% conversion of furfuryl alcohol was obtained with 90% selectivity to tetrahydrofurfuryl alcohol after reacted at 0.5 MPa H2, 303 K for 12 h. The Pd/UiO-66-v was proved to be effective for the hydrogenation of furan ring in furans and could be used for at least five times.Keywords:furfuryl alcohol;hydrogenation;tetrahydrofurfuryl alcohol;Pd/UiO-66-v;water solvent
研究领域:
催化化学
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生物质转化
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绿色化学
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产品关联
DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
·
2023
·
IF 8.4
Man Yang,Yuxiang Jiao,Jianglin Duan,Keying Wu,Hailiang Song,Shaodong Sun,Yujing Ren
Taking the background of the ambiguous role of oxophilic metal oxide in metal-acid bifunctional catalysts for the important field of tetrahydrofurfuryl alcohol (THFA) hydrogenolysis, a linear relationship between the W═O/W–OH content in sub-nano-Rh-supported WOx and 1,5-pentanediol (1,5-PeD) yields from THFA hydrogenolysis has been established. It reveals that the higher reduction temperature promotes the surface Rh/W ratio. Thus, hydrogen spillover is facilitated, leading to more surface W═O structures and thereby more in-situ-reduced W–OH generation. W–OH structures work as the active sites to provide in situ Brønsted acid, resulting in enhanced selective activation for secondary C–O bonds of THFA. This discovery reveals the unique role of the surface structure on oxophilic metal oxide in chemoselective hydrogenolysis of the secondary C–O bond in polyols.
研究领域:
催化化学
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材料科学
✓ 已验证
DOI
高影响因子
RSC Advances
·
2016
·Vol. 6
·期 56
·51221-51228
·
IF 3.289
Yanliang Yang,Jiping Ma,Xiuquan Jia,Zhongtian Du,Ying Duan,Jie Xu
Al2O3 modified by alkaline earth metals M–Al2O3 (M = Mg, Ca, Sr, Ba) was synthesised by coprecipitation method. The nickel-based catalysts supported by M–Al2O3 were prepared by impregnation method. The catalysts were characterized by TEM, N2 adsorption/desorption, XRD, H2-TPR, NH3-TPD and XPS, and used for the direct hydrogenation of furfural to tetrahydrofurfuryl alcohol (THFA) in water. The reaction was demonstrated to proceed through furfuryl alcohol as an intermediate. The modification of Al2O3 by alkaline earth metals has a significant effect on the activity and selectivity of THFA. A high yield of THFA was obtained over Ni/Ba–Al2O3 under optimized conditions. Moreover, the catalyst is recyclable and reusable at least four times without significant loss of the conversion of furfural and selectivity of THFA.
研究领域:
催化化学
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绿色化学
✓ 已验证
产品关联
DOI
高影响因子
ENERGY
·
2024
·
IF 9
Yingying Sheng,Fuping Tian,Xiang Wang,Ningyuan Jiang,Xinchi Zhang,Xiao Chen,Changhai Liang,Anjie Wang
The development of highly dispersed non-precious metal nanocatalysts is of great importance for the biomass hydrogenation. In this work, a precursor of Ni-citrate complex was formed by using cheap citric acid as a complexing agent and carbon source, and a highly dispersed nickel catalyst with a carbon-encapsulated structure was successfully prepared by a facile pyrolysis . The catalyst obtained at a pyrolysis temperature of 400 °C (Ni-CA-400) displayed a larger specific surface area, richer defect sites in the carbon layer , and uniform Ni nanoparticles (4.8 ± 0.7 nm). In the furfural (FAL) hydrogenation reaction, Ni-CA-400 delivered a high tetrahydrofurfuryl alcohol yield of 99.8 % under mild conditions (80 °C, 5 mmol FAL, 25 mg catalyst), maintaining relatively constant hydrogenation activity and Ni particle size in five consecutive cycles. The excellent catalytic performance and stability of Ni-CA-400 can be attributed to its unique carbon-encapsulated structure, which not only effectively avoids the migration and aggregation of active Ni particles during the preparation process, but also protects the metal Ni nanoparticles from oxidation in exposure to air. The kinetic studies showed that Ni-CA-400 exhibited high turnover frequency (TOF) for the hydrogenation of both C O and C C, making it a potential industrial catalyst for FAL hydrogenation.
研究领域:
化学工程
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催化材料
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生物质转化
✓ 已验证
产品关联
DOI
高影响因子
Catalysts
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2024
·Vol. 14
·期 7
·428
·
IF 3.8
Weiying Wang,Changlin Chen
Tetrahydrofurfuryl alcohol, a cost-effective biomass derivative, offers a sustainable path for synthesizing 1,5-pentanediol through hydrogenolysis. To develop the efficient production of 1,5-pentanediol from this alcohol, we have prepared a series of MgAl2O4-modified Pt/WOx/γ-Al2O3catalysts with varying compositions via impregnation–calcination methods. The physicochemical properties of these catalysts were subsequently characterized using diverse techniques. Characterization revealed that magnesia–alumina spinel modification enhanced Pt particle dispersion, CO adsorption on Pt/WOx/γ-Al2O3, reduced Pt particle reduction temperature, diminished the acid content in the catalysts, and increased the surface oxygen vacancy concentration. These alterations appear to influence the catalyst performance, though other factors cannot be ruled out. Catalytic activity tests demonstrated that magnesia–alumina spinel modification improved tetrahydrofurfuryl alcohol hydrogenolysis activity and the 1,5-pentanediol selectivity of Pt/WOx/γ-Al2O3. Optimal performance was achieved at 12% magnesia–alumina spinel loading, with a tetrahydrofurfuryl alcohol conversion of 47.3% and 1,5-pentanediol selectivity of 88.4%.
研究领域:
化学工程
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催化科学
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生物质转化
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2017
·
IF 2.843
Chuang Li,Guangyue Xu,Xiaohao Liu,Ying Zhang,Yao Fu
Tetrahydrofurfuryl alcohol (THFAL), as a green industrial solvent, can be obtained directly from biomass-derived furfural with 100% conversion and 100% yield over a hydroxyapatite-supported Pd catalyst (Pd-HAP) under relatively mild conditions (40 °C, 1 MPa H2, and 3 h) in 2-propanol. At room temperature and reacting for 8 h, the yield of THFAL was more than 99%. By capturing the intermediates, two pathways were proposed as follows: (1) Furfural was partially hydrogenated to furfuryl alcohol, and then, furfuryl alcohol was further hydrogenated to THFAL. (2) Furfural and 2-propanol first formed 2-(isopropoxymethyl)furan (2-IPMF) via etherification, and then, 2-IPMF was ultimately converted to THFAL. The Pd-HAP catalyst was characterized by various techniques including XRD, SEM, TEM, HAADF-STEM, XPS, and ICP-AAS. The results revealed that the outstanding catalytic performance of Pd-HAP was attributed to the quasicoordination effect between Pd and HAP, which not only contributed to highly dispersed and stable Pd nanoclusters but also led to better activation of hydrogen. The recyclability of the Pd-HAP catalyst was also investigated and proved its stability in the conversion of furfural and high selectivity toward THFAL.
研究领域:
生物化学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2023
·
IF 7.4
Wenqi Zhao,Xiaowei Bai,Xiangrui Lin,Yalkunjan Tur sun,Mei Zhong,Zhenghua Dai,Jian Li
Biomass-derived furfural and its derivatives are promising feedstocks for producing valuable C 5 diols by catalytic hydrolysis. However, this process requires selective ring opening of tetrahydrofurfuryl alcohol (THFA) to 1,5-pentanediol, which is challenging. Here we report efficient route for this conversion using Ni-La(OH) 3 catalysts prepared by a green co-precipitation-hydrothermal method. We show that these catalysts can achieve up to 91.7% yield and 94.6% selectivity of 1,5-pentanediol from THFA under mild conditions. We elucidate the key role of the La(OH) 3 phase, the basic sites and the Ni n+ -O-La 3+ structure of the catalysts in promoting the selective hydrogenolysis and ring opening of THFA. We also demonstrate that the co-dehydrogenation of secondary alcohols enables lower reaction pressure and longer catalyst lifetime. Our work provides a sustainable and environmentally benign approach for producing 1,5-pentanediol from biomass-based furfural and its derivatives, which has potential applications in polymer synthesis and green chemistry.
研究领域:
催化化学
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绿色化学
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可再生资源利用
✓ 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
研究领域:
催化化学
·
材料科学
·
绿色化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Huiling Zhang,Jingnan Yang,Teng Zhao,Fujun Lan,Yixin Luo,Fei Han,Xianliang Qiao,Qingxin Guan,Mo Qiu,Wei Li
Directional activation of oxygen-containing groups is a crucial challenge in the catalytic conversion of renewable biomass to high-value products. Herein, we fabricated uniform dispersed NiCo alloy nanoparticles by direct reduction flower-like layer double hydroxides (LDHs) precursors. The as-obtained Ni 2 Co 1 AlO exhibited outstanding yield (97.6 %) of tetrahydrofurfuryl alcohol (THFOL) in furfural hydrogenation, which is significantly superior to those of monometallic Ni-based (75 %) and Co-based (0 %) LDH catalysts and even higher than the most noble metal catalysts. The Ni 2 Co 1 AlO showed robust stability, e.g., the catalyst can be recycled up to 10 times without loss of its conversion and selectivity, which is attributed to the ultra-dispersed metal cations in layers and the confined effect of metal oxides. Characterizations and theoretical calculations demonstrate that alloying Ni with Co can downshift the d -band center of Ni in NiCo alloys, which facilitates the H* desorption to improve hydrogenation activity. The unique electronic interactions between Ni and Co facilitated the parallel adsorption of furfural while reduced the energy barriers of the furan ring hydrogenation, promoting the production of THFOL. This work provides a promising strategy of tailoring d -band center, which can shed light on the design of heterogeneous catalysts.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
DALTON TRANSACTIONS
·
2018
·Vol. 47
·期 48
·17276-17284
·
IF 4.099
Chun Chen,Ruoyu Fan,Wanbing Gong,Haimin Zhang,Guozhong Wang,Huijun Zhao
Water is inevitably associated with the production of bio-derived platform molecules, but most supported metallic catalysts have poor water compatibility. Although there have been a great number of investigations regarding the hydrogenation of bio-derived unsaturated compounds in the organic phase, the reactions that proceed in water are still quite challenging. Herein, we report the synthesis of a supported nickel catalyst (Ni-LN650) by the reduction of the perovskite-type oxide LaNiO3 precursor at 650 °C. The derived catalyst affords attractive activity in the hydrogenation of furfural by using water as the reaction medium, in which furfural is completely converted into tetrahydrofurfuryl alcohol with the highest productivity of 289.7 mmol gNi−1 h−1 at 120 °C and 1 MPa of H2 within 5 h of reaction. The Ni-LN650 catalyst also exhibits good stability and renewability in a cycle test, stemming from the self-regeneration peculiarity of the perovskite-type oxide precursor. Moreover, the catalyst can also demonstrate high activity in the aqueous-phase hydrogenation of various aldehydes, alkenes and carboxylic acids in a series of experiments. Due to the merits of usability in water, the renewability and wide application scope, the Ni-LN650 catalyst can be treated as a promising candidate for the catalytic conversion of bio-derived platform molecules into high value-added fuels and chemicals.
研究领域:
催化化学
·
可再生资源转化
·
绿色化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）