JOURNAL OF THE CHINESE CHEMICAL SOCIETY
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2019
·Vol. 66
·期 12
·1610-1618
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IF 1.188
Tao Wang,Aiyun Hu,Haijun Wang,Yongmei Xia
Layered double hydroxides (LDHs) and their derivatives have been reported to be widely used as heterogeneous catalysts in various reactions. Herein, Ni-Fe LDHs with the controlled Ni/Fe molar ratios (2:1, 3:1, 4:1) were synthesized via an easy hydrothermal method, which were used to catalyze the selective reduction of biomass-derived furfural into furfuryl alcohol using 2-propanol as a H-donor under autogenous pressure and characterized using FT-IR, XRD, TGA, BET, SEM, NH 3 -TPD, and CO 2 -TPD. It was found that the LDH with a Ni/Fe molar ratio of 3:1 demonstrated the best catalytic activity among the LDHs with different Ni/Fe molar ratios, which showed 97.0% conversion of furfural and 90.2% yield of furfuryl alcohol at 140°C for 5 hr. This was attributable to the synergistic effect of acidic sites and basic sites of the catalyst.
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Communications Chemistry
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2018
·Vol. 1
·期 1
·1-11
·
IF 0
Li Hu,Zhao Wenfeng,Saravanamurugan Shunmugavel,Dai Wenshuai,He Jian,Meier Sebastian,Yang Song,Riisager Anders
The production of liquid fuels and fine chemicals often involves multi-step reaction processes with selective hydrogenation as one of the key steps. This step most often depends on high-pressure excess hydrogen gas, fossil resources, and newly prepared metallic catalysts. Here we describe an approach to tune activity and selectivity toward transfer hydrogenation of renewable biomass derivatives over commercially available Pd/C using liquid hydrosilane as hydrogen source. The appropriate control of water-doping content, acid type, reaction temperature, and liquid H − donor dosage permits the selective formation of four different value-added products in high yields (≥90%) from bio-based furfural under mild reaction conditions (15–100 °C). Mechanistic insights into the hydrosilane-mediated cascade reactions of furfural are obtained using isotope labeling. The catalyst is recyclable and can selectively reduce an extensive range of aromatic carbonyl compounds to the corresponding alcohols or hydrocarbons in 83–99% yield, typically at 25–40 °C.
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APPLIED CATALYSIS A-GENERAL
·
2018
·
IF 4.521
Xiaoqian Guo,Feng Guo,Yishan Li,Zhangqin Zheng,Zhexu Xing,Zihan Zhu,Ting Liu,Xin Zhang,Ying Jin
Dehydration of D-xylose to yield furfural was carried out using bimetallic salts of a heteropolyacid as the catalyst at 160–220 °C in the DMSO/H 2 O mixtures. The effect of Sn/Cs molar ratio of the bimetallic salts of 12-tungstophosphoric acid (PW) obtained by ultrasound-assisted coprecipitation on dehydration of D-xylose was investigated. The resultant catalysts were characterized by X-ray diffraction, N 2 adsorption, field emission scanning electron microscopy and energy dispersive X-ray (EDX). It was found that the Sn-Cs codoped PW catalysts retained the Keggin crystal structure of PW. Sn 0.625 Cs 0.5 PW was the most active catalyst in the dehydration of D-xylose into furfural. The maximum D-xylose conversion (close to 100 wt %) and furfural yield (63 wt %) were achieved at 200 °C for 3 h in DMSO/H 2 O mixtures. It was found that 16.7 wt % Sn 0.625 Cs 0.5 PW on a chitosan-derived support displayed similar catalytic activity to that of Sn 0.625 Cs 0.5 PW and good stability after recycling six times.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2018
·
IF 11.698
Yueqing Wang,Guoqiang Ding,Xiaohai Yang,Hongyan Zheng,Yulei Zhu,Yongwang Li
The selective synthesis of furfural or hydroxymethylfurfural (HMF) from fructose on single catalyst (Beta zeolite, Hβ) is challenging task. However, in this study, selectivity of Hβ zeolite was discovered easily to tune by solvent effects. Strong solvent effects on the selectivity of fructose conversion were observed in different manners depending on the solvent used. It was shown that the coordinated state of framework aluminum, induced by solvent effects, has a major impact on the selectivity. The solvents with amide group were discovered to induce the reversible tetrahedral-octahedral framework aluminum transformation, but the configuration of aluminum was no influenced by other solvents such as γ-butyrolactone (GBL). Compared with other solvents, the GBL was not able to enhance turnover frequency (TOF) value of reaction but also suppress the degradation of furfural. Interestingly, a considerable yield of furfural (50.25%) was obtained combined with tetrahedral and octahedral framework aluminum active sites in GBL, while high selectivity of HMF (83.3%) was achieved in presence of single tetrahedral framework aluminum over Hβ in NMP.
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APPLIED CATALYSIS A-GENERAL
·
2019
·
IF 4.63
Shiqiu Zhang,Xue Yang,Kui Zheng,Ruihao Xiao,Qidong Hou,Bangjun Liu,Meiting Ju,Le Liu
It is a promising pathway to reduce the dependence on fossil fuels and obtain the bio-fuels or chemicals production from biomass derivatives. The conversion from furfural (FFR) to furfuryl alcohol (FFA) is an important industrial technology using the liquid-phase hydrogenation method with external hydrogen gas. However, the natural environment is threatened by the security of external hydrogen gas, toxicant catalyst, and the high energy consumption. Recently, in-situ hydrogenation is a novel method to converse FFR to FFA at mild reaction conditions to replace the dangerous external hydrogen gas. In this paper, we reported an efficient in-situ hydrogenation method via aqueous-phase reforming of methanol using Pt loading MgTiO 3 (perovskite-type material) at mild conditions. Pt nanoparticles were high dispersion on the nano-MgTiO 3 -450 surface, and CH 3 OH and H 2 O were reformed to produce hydrogen gas on the catalyst surface through the action of Pt nanoparticles. A part of active hydrogen could be involved in the reduction of Pt 2+ to Pt 0 , resulting in the perfect recyclability of the Pt@MT-450 catalyst. The other part of active hydrogen were participated in the hydrogenation of FFR conversion to FFA under the interaction of Pt and Mg elements. The in-situ hydrogenation of FFR to FFA using Pt@MT-450 is an effectively pathway to reduce the reaction conditions than that with external hydrogen gas.
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Green Energy & Environment
·
2017
·
IF 0
Fen Yue,Christian Marcus Pedersen,Xiuyin Yan,Yequn Liu,Danlei Xiang,Caifang Ning,Yingxiong Wang,Yan Qiao
Hydrothermal carbonization (HTC) is a valuable approach to convert furfural residue (FR) into carbon material. The prepared biochars are usually characterized comprehensively, while the stock process water still remains to be studied in detail. Herein, a NMR study of the main components in stock process water generated at different HTC reaction conditions was reported. Various qualitative and quantitative NMR techniques ( 1 H and 13 C NMR, 1 H– 1 H COSY and 1 H 13 C HSQC etc. ) especially 1D selective gradient total correlation spectroscopy (TOCSY NMR) were strategically applied in the analysis of HTC stock process water. Without separation and purification, it was demonstrated that the main detectable compounds are 5-hydroxymethylfurfural, formic acid, methanol, acetic acid, levulinic acid, glycerol, hydroxyacetone and acetaldehyde in this complicate mixture. Furthermore, the relationship between the concentration of major products and the reaction conditions (180–240 °C at 8 h, and 1–24 h at 240 °C) was established. Finally, reasonable reaction pathways for hydrothermal conversion of FR were proposed based on this result and our previously obtained characteristics of biochars. The routine and challenging NMR methods utilized here would be an alternative other than HPLC or GC for biomass conversion research and can be extended to more studies.
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
·
IF 8.1
Aozhou Wang,Kaisheng Yao,Shuaibo Li,Qi Wang,Tianhang Han,Weiwei Lu,Haili Zhao
Furfuryl alcohol (FA) is an important chemical and has extensive applications in varied fields. To realize the highly selective hydrogenation of furfural (FF) to produce FA, the key is the preparation of the catalysts with excellent performance. Herein, a very simple wet chemical method is developed for the one-step preparation of PdAg nanosponges (NSs). Specifically, with Pd(OAc) 2 and AgNO 3 as precursors, and ethylene glycol (EG) as both solvent and reducing agent, PdAg NSs can be grown and assembled at mild temperature of 40 °C. Throughout the reaction, no any surfactants and additional reducing agents are applied. The as-prepared PdAg NSs possess 3D self-supported alloy structures, “clean” surface, abundant pores, high specific surface area and rich defects. In the FF hydrogenation reaction at 60 °C under 1.5 MPa H 2 pressure in the mixed solvent of ethanol and water (1 : 4 in volume ratio), the self-supported PdAg-1 NSs (1 : 1 in Pd/Ag molar ratio) exhibit superior catalytic performance than other PdAg NSs, pure Pd sample and commercial Pd/C (10%). With PdAg-1 NSs as catalyst in the absence of support, 100% FF can be converted and the selectivity toward FA is as high as 97.1% at 36.0 h of reaction. After 4 cycles, PdAg-1 NSs still maintain the high catalytic activity in FF hydrogenation and high selectivity toward FA, which may originate from the 3D self-supported structures, high specific surface area, “clean” surface, rich defects and electronic synergistic effect between Pd and Ag. This simple fabrication of PdAg NSs introduces new ideas for the synthesis of other nanostructured bi- and multi-metallic catalysts for highly selective FF hydrogenation to FA and other advanced applications.
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Journal of Materials Chemistry A
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2024
·
IF 10.7
Yuhui Huang,Yehan Tao,Qingqing Wang,Jian Du,Jinwen Hu,Jie Lu,Yanna Lv,Haisong Wang
To develop an industrial zeolite-based catalyst for efficient furfural production, the acidity, pore structure, and electronic properties of H-β zeolite were modulated by synergistic deatomization and atomic implantation treatments. The dealumination effectively decreased the intrinsic aluminum-related Lewis and Brosted acid sites, thus decreasing the occurrence of unwanted side reactions. Meanwhile, the removed skeleton aluminum can create voids for the following atomic implantation of introducing higher valent-state niobium species, which would provide new kinds of catalytic active sites, increase the average pore size by distorting the zeolite skeleton, and enhance the interaction with reactant molecules by acting as more electron deficient centers. In a single-phase water/γ-valerolactone reaction system, the optimum catalyst can efficiently convert both xylan and xylose with a conversion of 100 % at a medium temperature of 130 ℃ within 3 hours. Compared with the furfural yield over untreated H-β (12.7%), the yield over deAlβ/Nb(20%) catalyst was greatly enhanced by 54% with xylose as raw material. The catalyst can be recovered by simple cleaning and thermal regeneration and then reused. The proposed post-treatment strategy could maintain the integrity of the zeolite structure, ensure uniform and stable metal dispersion under harsh conditions, manage the complexity and cost of the preparation process, and most importantly, optimize the catalytic performance. Addressing these issues is essential for improving the efficiency and practical application of industrial zeolite catalysts by this general approach and benefiting industrial furfural production.
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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.
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ChemSusChem
·
2016
·Vol. 9
·期 11
·1339-1347
·
IF 7.116
Jiang Li,Jun-ling Liu,Hong-jun Zhou,Yao Fu
Graphical FF to FFA with Fe : Efficient catalytic transfer hydrogenation of furfural (FF) to furfuryl alcohol (FFA) over heterogeneous iron catalysts is demonstrated for the first time. Iron cations coordinated by pyridinic nitrogen functionalities on the carbon support are possibly responsible for the enhanced catalytic activity. This paves the way for achieving biomass conversion through heterogeneous iron catalysis. Iron-based heterogeneous catalysts, which were generally prepared by pyrolysis of iron complexes on supports at elevated temperature, were found to be capable of catalyzing the transfer hydrogenation of furfural (FF) to furfuryl alcohol (FFA). The effects of metal precursor, nitrogen precursor, pyrolysis temperature, and support on catalytic performance were examined thoroughly, and a comprehensive study of the reaction parameters was also performed. The highest selectivity of FFA reached 83.0 % with a FF conversion of 91.6 % under the optimal reaction condition. Catalyst characterization suggested that iron cations coordinated by pyridinic nitrogen functionalities were responsible for the enhanced catalytic activity. The iron catalyst could be recycled without significant loss of catalytic activity for five runs, and the destruction of the nitrogen–iron species, the presence of crystallized Fe 2 O 3 phase, and the pore structure change were the main reasons for catalyst deactivation.
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PubMed
高影响因子
ACS Catalysis
·
2016
·
IF 9.307
Da Lei,Kai Yu,Meng-Ru Li,Yuling Wang,Qi Wang,Tong Liu,Pengkun Liu,Lan-Lan Lou,Guichang Wang,Shuangxi Liu
Single-crystalline Pd nanocrystals enclosed by {111} or {100} facets with controllable sizes were synthesized and originally employed as catalysts in the aerobic oxidation of 5-hydroxymethyl-2-furfural (HMF). The experimental results indicated that the particle size and exposed facet of Pd nanocrystals could obviously influence their catalytic performance. The size-dependent effect of Pd nanocrystals in this reaction could only be derived from the different Pd dispersions. Therefore, the facet effect of Pd nanocrystals was first investigated in this work through experimental and theoretical approaches. It was found that Pd-NOs enclosed by {111} facets were more efficient than Pd-NCs enclosed by {100} facets for the aerobic oxidation of HMF, especially for the oxidation step from 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) toward 5-formyl-2-furancarboxylic acid (FFCA). The TOF value of Pd-NOs(6 nm) was 2.6 times as high as that of Pd-NCs(7 nm) and 5.2 times higher than that of commercial Pd/C catalyst for HMF oxidation. Through density functional theory (DFT) calculations, the notably enhanced catalytic performance of Pd-NOs could be mainly attributed to the lower energy barrier in the alcohol oxidation step (from HMFCA to FFCA) and higher selectivity for O2 hydrogenation to produce peroxide.
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Biomass Conversion and Biorefinery
·
2024
·
IF 3.5
Li Yihui,Zhong Zhaoping,Wang Wei,Ye Qihang,Zheng Xiang,Liu Hengyuan,Yun Zekun
The valorization of cellulose in lignocellulose into high-value products is a crucial step in biorefinery processes. In this study, FeCl 3 ·6H 2 O was impregnated and supported on a carbon-based substrate, followed by carbonization and sulfonation to prepare the composite carbon-based solid acid. The resulting composite carbon-based solid acid was used as the catalyst, while γ-valerolactone, a lactone solvent, served as the reaction medium for producing furfural as the product from cellulose. When using this catalytic system to treat cellulose, under appropriate reaction temperature and residence time, the yield of furfural reached 75.26%, while the conversion rate of cellulose was 99.8%. Characterization techniques including SEM, EDS, XRD, XPS, and Py-FTIR were employed to confirm that the composite carbon-based solid acid possessed Brønsted acid sites, Lewis acid sites, and -Cl active groups, all of which exhibited excellent catalytic activity and selectivity towards furfural production. Furthermore, the synergistic effect between the catalytic activity of the three active groups in the carbon-based solid acid and the inhibitory effect of the nonpolar solvent on side reactions contributed to the outstanding performance of the catalytic system. And this study proposes a possible reaction pathway for the conversion of cellulose to furfural. This research provides an efficient pathway for the valorization of cellulose and holds significance in furfural production and biomass conversion. Graphical abstract
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