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NC600 derived from ZIFW-8
Molecular Catalysis 480 (2020) 110651
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Highly selective hydrogenation of furfural and levulinic acid over Ni0.09Zn/ NC600 derived from ZIFW-8
T
Zhi-Xin Lia, Xian-Yong Weia,b,⁎, Guang-Hui Liua, Xing-Long Menga, Zheng Yanga, Shuo Niua, Di Zhanga, Hua-Shuai Gaoa, Zhi-Hao Maa, Zhi-Min Zonga a b
Key Laboratory of Coal Processing and Efficient Utilization, Ministry of Education, China University of Mining & Technology, Xuzhou, 221116, Jiangsu, China State Key Laboratory of High-efficiency Coal Utilization and Green Chemical Engineering, Ningxia University, Yinchuan, 750021, Ningxia, China
ARTICLE INFO
ABSTRACT
Keywords: Furfural Levulinic acid Selective hydrogenation Zeolitic imidazolate frameworks Ni0.09Zn/NC600
Highly selective hydrogenation of furfural and levulinic acid (LA) was studied over Ni0.09Zn/NC600 derived from zeolitic imidazolate frameworks. The existence of active Ni3ZnC0.7 particles in Ni0.09Zn/NC600 was confirmed by multiple characterizations. As a result, over Ni0.09Zn/NC600, 99.7% of furfural conversion (FC) and 100% of furan-2-ylmethanol selectivity (FMS) were achieved in isopropanol (IP) at 170 °C for 2 h, while FC and (tetrahydrofuran-2-yl)methanol (THFM) selectivity are 97.5% and 86.4% in water at 150 °C for 1 h. Over the same catalyst, LA was completely converted to γ-valerolactone in water at 95 °C for 0.5 h. The catalyst is still highly active after 6 cycles of recycling with 92.8% of FC and 100% of FMS in IP at 170 °C for 1.5 h and 90.1% of LA conversion and 100% of γ-valerolactone selectivity in water at 80 °C for 0.5 h.
1. Introduction Nowadays, the research for upgrading bio-derivates, especially bioderived furfural and levulinic acid (LA), to chemicals and fuels has received considerable attention [1,2]. Furfural obtained from corncob with a variety of reactive bonds could be selectively hydrogenated to furan-2-ylmethanol (FM), (tetrahydrofuran-2-yl)methanol (THFM), 2methylfuran (2-MF), LA, γ-valerolactone (VL), and/or cyclopentanone [3–7]. However, highly selective hydrogenation of furfural is still a problem. FM is used to produce alkyl levulinates, LA, VL, resins, biofuels, and fuel additives [7,8], while the uses of THFM include as a solvent for coating or resin and as a raw material to produce a variety of chemicals, such as pentane-1,5-diol, succinic acid, pentaerythritol, and pyranoid [9–11]. Furfural hydrogenation (FH) to FM was widely reported over either non-noble metals in liquid phase, such as Cu [12], Co [13], Ni [14], Cu-Cr [15], and Cu-Co [16], or noble metals, such as Pd [17], Pt [18], and Pd-Cu [19]. In addition, FH to THFM was intensively studied over various catalysts including Ru [10], Pd [10], Pt [11], and Ni [20]. However, since activity, selectivity, and stability of these catalysts cannot be simultaneously achieved at a low cost, there is no satisfactory catalyst for highly selective FH to FM or THFM. LA is a basic raw material to produce VL, pentane-1,4-diol, 2-methyltetrahydrofuran, and 5-nonanone [21–24]. Remarkably, VL is not
only a food additive but also a potentially ideal green solvent [25,26]. Furthermore, VL has attractive applications as a versatile intermediate for producing renewable fuels and chemicals [27–29]. However, although a variety of catalysts, such as Ni [30], Cu [31], and Ru [32], were widely used in LA hydrogenation (LAH) to VL, they have many disadvantages, such as low activity, poor selectivity, and need of relatively harsh reaction conditions. Selectively LAH to VL under mild conditions still faces challenges. With these in mind, developing a catalyst with highly selective FH and LAH is still insistent demands. Bimetallic Ni catalysts have been widely used in energy and biomass upgrading fields due to their low price and high hydrogenation activity [33,34]. In addition, carbon-based metal nanoparticles derived from newly emerging zeolitic imidazolate frameworks (ZIFWs) are extensively applied in many fields [35–39]. Notably, the metal center of ZIFWs is partially reduced as metal nanoparticles under high-temperature inert gas which is embedded in a ZIFWs-derived carbon material [38,39]. In addition, the nitrogen contained in ZIFWs is also embedded in the carbon material, which could interact with metal nanoparticles to improve the catalytic performance [40,41]. Inspired by these advances, developing a high performance catalyst derived from ZIFWs is indispensable for FH to FM or THFM and LAH to VL. In this work, we prepare a Ni0.09Zn/NC by calcining Ni0.09/ZIFW-8. The catalyst shows excellent catalytic performances for selective FH to
⁎ Corresponding author at: Key Laboratory of Coal Processing and Efficient Utilization, Ministry of Education, China University of Mining & Technology, Xuzhou, 221116, Jiangsu, China. E-mail address: [email protected] (X.-Y. Wei).
https://doi.org/10.1016/j.mcat.2019.110651 Received 25 July 2019; Received in revised form 20 September 2019; Accepted 30 September 2019 2468-8231/ © 2019 Elsevier B.V. All rights reserved.
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Fig. 1. XRD patterns of the samples.
FM in isopropanol (IP) or to THFM in water and LAH to VL in water.
2.4. Catalytic reaction
2. Experimental
A substrate (50 μL), a NixZn/NCy (50 mg), and a solvent (10 mL) are added to an 60 mL magnetically stirred autoclave. After replacing air in the autoclave with N2, a certain amount of hydrogen was filled into the autoclave. Then, the autoclave was heated to a required temperature and maintained at the temperature for an indicated period of time at 150 rpm.
2.1. Materials Furfural (99.0%), LA (99.0%), FM (99.0%), THFM (99.0%), VL (99.0%), IP, hexane, ethanol, methanol, butanol, 2-methylimidazole, Ni (NO3)2•6H2O, and Zn(NO3)2•6H2O were purchased from Aladdin Industrial Inc., Shanghai, China and used without purification. N2 and H2 used are highly pure gases.
3. Results and discussion 3.1. Catalyst characterization
2.2. Catalyst preparation
The diffraction peaks shown in Fig. 1 at 31.7°, 34.4°, 36.3°, 47.5°, 56.6°, 62.8°, 66.4°, 67.9°, and 69.7° are attributed to representative diffractions of planes (100), (002), (101), (102), (110), (103), (200), (112), and (201) of crystalline ZnO, respectively (PDF#36-1451), while the characteristic diffraction peaks located at 42.7°, 49.7°, 73.1°, and 88.5° can be attributed to representative diffraction of planes (111), (200), (220), and (311) of Ni3ZnC0.7 (PDF#28-0713), respectively. The diffraction peaks of Ni3ZnC0.7 were significantly enhanced with increasing Ni loading. Transmission electron microscopic images (Fig. S1) of NixZn/NC600 also show that the number of Ni3ZnC0.7 particles increased significantly with increasing Ni content. As observed from TG curves, Ni0.09/ZIFW-8 rapidly decomposed with raising the temperature to 320 °C under flow N2 (Fig. S2). Hence, Ni0.09Zn/NCy were prepared at 400, 500, 600, and 700 °C. The diffraction peaks of ZnO and Ni3ZnC0.7 increased with raising CT, indicating that the crystal sizes of ZnO and Ni3ZnC0.7 tend to increase at higher temperatures (Fig. 1). Ni, Zn, N, C, O, NiO, and ZnO were confirmed to exist in Ni0.09Zn/ NC600 (Table S1, Figs. 2 and S3). Peaks for Ni 2p1/2 at 870.1 eV and Ni 2p3/2 at 852.8 eV correspond to metallic Ni and peaks of Ni 2p1/2 at 871.6 and 873.0 eV and Ni 2p3/2 at 854.8, 855.8, 857.3, 858.9, and 861.2 eV could be attributed to NiO [42–44], while the peaks of Ni 2p3/ 2 at 853.6 eV suggest the existence of the carbide phase in the carbon composite [45,46] (Fig. 2). The peak at 1021.8 eV was also identified corresponding to ZnO (Fig. S3) [47]. Ni0.09Zn/NC600 contains pyridine
2.2.1. Preparation of ZIFW-8 Typically, 10.4 g Zn(NO3)2•6H2O and 7.4 g 2-methylimidazole are dissolved in 65 mL and 50 mL water, respectively [38,41]. Then, the former is quickly poured into the latter one with rapidly appearing white precipitates. After being stirred at 30 °C for 12 h, ZIFW-8 is collected by centrifugation, washed with water and ethanol sequentially, and dried at 80 °C in vacuum for 12 h. 2.2.2. Preparation of Nix/ZIFW-8 Typically, 2.47 g Ni(NO3)2•6H2O is dissolved in 70 mL ethanol. Then, 5.00 g ZIFW-8 is dispersed in the Ni(NO3)2•6H2O/ethanol solution followed by agitation at 30 °C for 12 h to obtain Ni0.09/ZIFW-8 by subsequent filtration, washing, and drying. Other Nix/ZIFW-8 species were prepared in the same way, where x represents the molar ratio of Ni to Zn (x = 0.01, 0.05, 0.09, and 0.13). 2.2.3. Preparation of NixZn/NCy Typically, Ni0.09Zn/NC600 is prepared by calcining Ni0.09/ZIFW-8 under N2 at 600 °C for 5 h. Other NixZn/NCy species were prepared in the same way, where x represents the molar ratio of Ni to Zn (x = 0.01, 0.05, 0.09, and 0.13) and y represents the calcination temperature (CT) of Nix/ZIFW-8 (y = 400, 500, 600, and 700 °C). 2.2.4. Preparation of Zn/NC and Ni/NC Zn/NC and Ni/NC were prepared by calcining ZIFW-8 and Ni-ZIFW, respectively, under N2 at 600 °C for 5 h. 2.3. Characterization techniques Each catalyst structure was characterized with a Hitachi S-3700 N scanning electron microscope combined with an energy dispersive spectrometer (EDS), a JEM-2100 microscope transmission electron microscope, an ESCALAB 250 X-ray photoelectron spectroscope, a Bruker Advance X-ray diffraction (XRD), a Nicolet Magna IR-560 Fourier transform infrared spectrometer, a TP-5000 multi-function NH3 temperature-programmed desorption (NH3-TPD) instrument, a TA SDTQ600 thermo gravimetric (TG) analyzer, and a laser ablation inductively coupled plasma mass spectrometer (LA/ICPMS).
Fig. 2. X-ray photoelectron spectrum of Ni0.09Zn/NC600. 2
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Fig. 3. Scanning electron microscopic images of ZIFW-8, Ni0.09/ZIFW-8, and Ni0.09Zn/NC600.
nitrogen and graphite nitrogen, which could increase the metal dispersion in the catalyst (Fig. S2) [48,49]. The formation of ZIFW-8 was confirmed in Fig. S4. ZIFW-8 with clearly smooth surface and particle sizes of around 1.5 μm was observed in Figs. 3 and S5. Ni0.09/ZIFW-8 was prepared by impregnating Ni with ZIFW-8 in ethanol. Its rough surface is evenly distributed with holes, facilitating better metal dispersion in the prepared Ni0.09Zn/NC600 by subsequent calcination (Figs. 3 and 4). In addition, as Fig. 3 shows, Ni0.09Zn/NC600 maintains the basic structure of Ni0.09/ZIFW-8, but its surface obviously collapses partially and becomes rougher. The uniform distribution of Ni, Zn, N, C, and O in Ni0.09Zn/NC600 shown in Fig. S6 indicates that the nitrogen element was successfully inset into Ni0.09Zn/ NC600. The uniform dispersion of Ni3ZnC0.7 particles was also observed in Fig. 4. The particle size of Ni3ZnC0.7 gradually increased with raising
CT, which is consistent with the XRD analysis (Fig. 4). The lattice spacing (0.215 nm) corresponds to the d(111) in Ni3ZnC0.7, confirming the existence of Ni3ZnC0.7 [41].
Fig. 4. Transmission electron microscopic images of the samples.
Fig. 5. Transmission electron microscopic images of Ni0.09Zn/NC600.
3.2. FH to FM over Ni0.09Zn/NC600 3.2.1. Effects of the molar ratio of Ni to Zn in NixZn/NC600, CT of Ni0.09/ ZIFW-8, and solvent on FH over Ni0.09Zn/NC600 Table S2 shows that FH did not proceed over Zn/NC, while Ni/NC led to the excessive FH, resulting in low FM selectivity (FMS). In IP, furfural was not hydrogenated over Ni0.01Zn/NC600. FM is the only product from FH over Ni0.05Zn/NC600, Ni0.09Zn/NC600, and Ni0.13Zn/ NC600, and FC increased with increasing Ni/Zn molar ratio in the catalyst, since a lot of Ni3ZnC0.7 was formed by the interaction between Ni and Zn/NC. In water, both FC and THFM selectivity (THFMS) increased with increasing Ni/Zn molar ratio up to 0.09 in NixZn/NC600, but further increase in Ni/Zn molar ratio decreased THFMS (Table S3). Similar tendancy for LA conversion (LAC) was also observed in Table S4, while VL is the only product from LAH (Fig. 5). As displayed in Fig. 6, FC increased to ca. 99% with raising the CT to 600 °C in IP. However, at higher CTs, FC dramatically dropped, perhaps due to the increase in Ni3ZnC0.7 particle size in Ni0.09Zn/NC700 (Figs. 4 and 6a). As shown in Fig. 7, relatively high FMSs were obtained in moderately polar solvents over Ni0.09Zn/NC600. FH did not proceed in hexane and is difficult in methanol and ethanol. Although FC is near 100% and
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3.2.2. Effects of reaction parameters on FH to FM over Ni0.09Zn/NC600 As Fig. 9 displays, FC increased up to almost 100% with prolonging time to 2 h, raising temperature to 170 °C, and increasing initial hydrogen pressure (IHP) to 2 MPa, while FM is the only product in FH.
Fig. 6. CT effect of Ni0.09/ZIF-8 on FH over Ni0.09Zn/NCy under 2 MPa of IHP at 170 °C for 2 h in IP.
Fig. 7. Solvent effect on FH over Ni0.09Zn/NC600 under 2 MPa of IHP at 170 °C for 2 h.
Fig. 8. NH3-TPD of Ni0.09Zn/NC600.
FMS is very low in water, more THFM was produced. This could be related to different activation capacities of active components to H2 in different polar solvents and solvent-reactant interactions could also be affected the hydrogenation activity [16,19]. In addition, tetrahydrofuran-2-carbaldehyde (THFC) was not found in all the products (Table S5). As shown in Fig. 8, Ni0.09Zn/NC600 has strong acidic sites, facilitating both the formation of H+ from H2 and furfural adsorption on Ni0.09Zn/NC600 [50,51]. The > C=O group in furfural should be more easily adsorbed, activated, and hydrogenated initiated by H+ addition to the oxygen atom in > C=O [52,53]. Therefore, Ni0.09Zn/ NC600 was used to explore FC, FMS, and THFMS in IP or water. Ni0.09Zn/NC is used to denote Ni0.09Zn/NC600 in the Figures and Tables of the Supporting Material for convenience in typesetting.
Fig. 9. FH to FM over Ni0.09Zn/NC600 in IP ((a) IHP 2 MPa, 2 h; (b) IHP 2 MPa, 170 °C (c) 170 °C, 2 h; (d) IHP 2 MPa, 170 °C, 1.5 h). 4
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abstraction from the catalyst surface, H…H transfers to the furan ring, and > C–O– bond cleavage in tetrahydrofuran ring of THFM.
3.3. FH to THFM over Ni0.09Zn/NC600 in water A high THFMS was achieved by adjusting the reaction conditions. As shown in Fig. 10a, FH at lower temperatures (70 and 90 °C) has higher FMSs up to 100%. Nevertheless, with raising temperature from 90 to 150 °C, although FC increased, FMS decreased sharply, while THFMS increased rapidly and then decreased with raising temperature to 170 °C. In addition, the selectivity of other products shows a trend of gradual increase due to gradual decomposition of THFM at high temperatures. By prolonging reaction time, THFMS first increased rapidly and then decreased from 20 to 100 min, while the corresponding FMS decreased sharply (Fig. 10b). Similarly, the selectivity of other products decreased with prolonging time. These results also support the possibility that other products were derived from THFM decomposition. The selective hydrogenation of FM to THFM over Ni0.09Zn/NC600 was confirmed and THFC was never detected (Table S5). As illustrated in Scheme 1, FH proceeds via H+ addition to the oxygen atom in > C=O of furfural, H−
3.4. The leaching and reusability of Ni0.09Zn/NC600 for FH to FM in IP As summarized in Fig. S7, FC does not increase in IP after removing Ni0.09Zn/NC600, suggesting that active sites of Ni0.09Zn/NC600 were not lost. LA/ICPMS analysis also shows that Ni or Zn leaching is negligible
Fig. 11. XRD patterns of Ni0.09Zn/NC600 after 6 times of recycle.
Fig. 10. FH over Ni0.09Zn/NC600 in water under 2 MPa of IHP.
Fig. 12. LAH to VL over Ni0.09Zn/NC600 in water ((a) IHP 2 MPa, 65 °C; (b) IHP 2 MPa, 30 min; (c) IHP 2 MPa, 80 °C, 30 min).
Scheme 1. Possible mechanisms for the selective FH over Ni0.09Zn/NC600. 5
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in the reaction solution (Table S1). As exhibited in Fig. 9d and Table S7, FC only slightly decreased and FMS remains at 92.8% over Ni0.09Zn/NC600 recycled 6 times. Ni0.09Zn/ NC600 is more stable than other catalysts reported (Table S7). XRD analysis suggests that the structure of Ni0.09Zn/NC600 remains almost no change after 6 cycles (Fig. 11).
[15] [16] [17]
3.5. LAH to VL over Ni0.09Zn/NC600
[18]
As shown in Fig. 12, LAC gradually increased with raising reaction temperature from 35 to 95 °C or prolonging reaction time from 0 to 75 min, while VL selectivity remains at 100%, indicating that Ni0.09Zn/ NC600 has excellent performance for specific LAH to VL. In addition, even after 6-times recycle, the activity of Ni0.09Zn/NC600 is still at a high level compared with reported catalysts (Table S8 and Fig. 12).
[19] [20] [21]
4. Conclusions
[22]
Ni0.09Zn/NC600 obtained by calcining Ni0.09/ZIFW-8 is highly active for selective FH to FM or THFM and LAH to VL, and still active after being recycled six times. The main products from FH over Ni0.09Zn/ NC600 are FM in IP and THFM in water.
[23] [24]
Acknowledgement
[25]
This work was supported by the Key Project of Joint Fund from the National Key Research and Development Program of China (Grant 2018YFB0604602).
[26]
Appendix A. Supplementary data
[27]
Supplementary material related to this article can be found, in the online version, at doi:https://doi.org/10.1016/j.mcat.2019.110651.
[28]
References
[29] [30]
[1] J.C. Serrano-Ruiz, J.A. Dumesic, Catalytic routes for the conversion of biomass into liquid hydrocarbon transportation fuels, Energ. Environ. Sci. 4 (2011) 83–99. [2] K. Tomishige, Y. Nakagawa, M. Tamura, Selective hydrogenolysis and hydrogenation using metal catalysts directly modified with metal oxide species, Green Chem. 19 (2017) 2876–2924. [3] S. Dutta, S. De, B. Saha, M.I. Alam, Advances in conversion of hemicellulosic biomass to furfural and upgrading to biofuels, Catal. Sci. Technol. 2 (2012) 2025–2036. [4] K. Yan, G. Wu, T. Lafleur, C. Jarvis, Production, properties and catalytic hydrogenation of furfural to fuel additives and value-added chemicals, Renew. Sust. Energ. Rev. 38 (2014) 663–676. [5] X. Li, P. Jia, T. Wang, Furfural: A Promising Platform Compound for Sustainable Production of C4 and C5 Chemicals, ACS Catal. 6 (2016) 7621–7640. [6] Y. Wang, S.Y. Sang, W. Zhu, L.J. Gao, G.M. Xiao, CuNi@C catalysts with high activity derived from metal-organic frameworks precursor for conversion of furfural to cyclopentanone, Chem. Eng. J. 299 (2016) 104–111. [7] E.A. Uslamin, N.A. Kosinov, E.A. Pidko, E.J.M. Hensen, Catalytic conversion of furanic compounds over Ga-modified ZSM-5 zeolites as a route to biomass-derived aromatics, Green Chem. 20 (2018) 3818–3827. [8] K. Yan, T. Lafleura, G.S. Wu, J.Y. Liao, C. Ceng, X.M. Xie, Highly selective production of value-added γ-valerolactone from biomass-derived levulinic acid using the robust Pd nanoparticles, Appl. Catal. A-Gen. 468 (2013) 52–58. [9] B. Pholjaroen, N. Li, Y. Huang, L. Li, A. Wang, T. Zhang, Selective hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol over vanadium modified Ir/SiO2 catalyst, Catal. Today 245 (2015) 93–99. [10] N. Merat, C. Godawa, A. Gaset, High selective production of tetrahydrofurfuryl alcohol: catalytic hydrogenation of furfural and furfuryl alcohol, J. Chem. Technol. Biot. 48 (2007) 145–159. [11] S. Bhogeswararao, D. Srinivas, Catalytic conversion of furfural to industrial chemicals over supported Pt and Pd catalysts, J. Catal. 327 (2015) 65–77. [12] C.P. Jiménez-Gómez, J.A. Cecilia, F.I. Franco-Duro, M. Pozo, R. Moreno-Tost, P. Maireles-Torres, Promotion effect of Ce or Zn oxides for improving furfuryl alcohol yield in the furfural hydrogenation using inexpensive Cu-based catalysts, Mol. Catal. 455 (2018) 121–131. [13] M. Audemar, C. Ciotonea, K. De Oliveira Vigier, S. Royer, A. Ungureanu, B. Dragoi, E. Dumitriu, F. Jerome, Selective hydrogenation of furfural to furfuryl alcohol in the presence of a recyclable Cobalt/SBA-15 catalyst, ChemSusChem 8 (2015) 1885–1891. [14] H. Jeong, C. Kim, S. Yang, H. Lee, Selective hydrogenation of furanic aldehydes
[31] [32] [33] [34] [35] [36] [37] [38] [39] [40]
[41] [42]
6
using Ni nanoparticle catalysts capped with organic molecules, J. Catal. 344 (2016) 609–615. K. Yan, A.C. Chen, Efficient hydrogenation of biomass-derived furfural and levulinic acid on the facilely synthesized noble-metal-free Cu-Cr catalyst, Energ. 58 (2013) 357–363. Y. Wang, Y.N. Miao, S. Li, L.J. Gao, G.M. Xiao, Metal-organic frameworks derived bimetallic Cu-Co catalyst for efficient and selective hydrogenation of biomass-derived furfural to furfuryl alcohol, Mol. Catal. 436 (2017) 128–137. G.M. Wang, R.L. Yao, H.Y. Xin, Y.J. Guan, P. Wu, X.H. Li, At room temperature in water: efficient hydrogenation of furfural to furfuryl alcohol with a Pt/SiC-C catalyst, RSC Adv. 8 (2018) 37243–37253. C. Nguyen-Huy, J.S. Kim, S. Yoon, E. Yang, J.H. Kwak, M.S. Lee, K. An, Supported Pd nanoparticle catalysts with high activities and selectivities in liquid-phase furfural hydrogenation, Fuel 226 (2018) 607–617. K. Fulajtárova, T. Soták, M. Hronec, I. Vávra, E. Dobrock, M. Omastová, Aqueous phase hydrogenation of furfural to furfuryl alcohol over Pd-Cu catalysts, Appl. Catal. A-Gen. 502 (2015) 78–85. L. Liu, H. Lou, M. Chen, Selective hydrogenation of furfural to tetrahydrofurfuryl alcohol over Ni/CNTs and bimetallic CuNi/CNTs catalysts, Int. J. Hydrogen Energ. 41 (2016) 14721–14731. C. Xiao, T.W. Goh, Z. Qi, S. Goes, K. Brashler, C. Perez, W. Huang, Conversion of levulinic acid to γ-Valerolactone over few-layer graphene-supported ruthenium catalysts, ACS Catal. 6 (2016) 593–599. J.L. Cui, J.J. Tan, Y.L. Zhu, F.Q. Cheng, Aqueous hydrogenation of levulinic acid to 1,4-pentanediol over Momodified Ru/AC catalyst, ChemSusChem 11 (2018) 1316–1320. J.C. Serrano-Ruiz, D. Wang, J.A. Dumesic, Catalytic upgrading of levulinic acid to 5nonanone, Green Chem. 12 (2010) 574–577. Z.B. Xie, B.F. Chen, H.R. Wu, M.Y. Liu, H.Z. Liu, J.L. Zhang, G.Y. Yang, B.X. Han, Highly efficient hydrogenation of levulinic acid into 2-methyltetrahydrofuran over Ni-Cu/Al2O3-ZrO2 bifunctional catalysts, Green Chem. 21 (2019) 606–613. D.M. Alonso, S.G. Wettstein, J.A. Dumesic, Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass, Green Chem. 15 (2013) 584–595. S. Dutta, I.K.M. Yu, D.C.W. Tsang, Y.H. Ng, Y.S. Ok, J. Sherwood, J.H. Clark, Green synthesis of gamma-valerolactone (GVL) through hydrogenation of biomass-derived levulinic acid using non-noble metal catalysts: a critical review, Chem. Eng. J. 372 (2019) 992–1006. K. Dhanalaxmi, R. Singuru, S. Mondal, L. Bai, B.M. Reddy, A. Bhaumik, O. Mondal, Magnetic nanohybrid decorated porous organic polymer:synergistic catalyst for high performance levulinic acid hydrogenation, ACS Sustain. Chem. Eng. 5 (2017) 1033–1045. J.P. Lange, R. Price, P.M. Ayoub, J. Louis, L. Petrus, L. Clarke, H. Gosselink, Valeric biofuels: a platform of cellulosic transportation fuels, Angew. Chem. Int. Ed. Engl. 49 (2010) 4479–4483. K. Yan, A. Chen, Selective hydrogenation of furfural and levulinic acid to biofuels on the ecofriendly Cu–Fe catalyst, Fuel 115 (2014) 101–108. S. Song, S.K. Yao, J.H. Cao, L. Di, G.J. Wu, N.J. Guan, L.D. Li, Heterostructured Ni/ NiO composite as a robust catalyst for the hydrogenation of levulinic acid to γvalerolactone, Appl. Catal. B-Environ. 217 (2017) 115–124. Q. Xu, X.L. Li, T. Pan, C.G. Yu, J. Deng, Q.X. Guo, Y. Fu, Supported copper catalysts for highly efficient hydrogenation of biomass-derived levulinic acid and [gamma]valerolactone, Green Chem. 18 (2016) 1287–1294. O.A. Abdelrahman, A. Heyden, J.Q. Bond, Analysis of kinetics and reaction pathways in the aqueous-phase hydrogenation of levulinic acid to form γ-Valerolactone over Ru/C, ACS Catal. 4 (2014) 1171–1181. S. De, J.G. Zhang, R. Luque, N. Yan, Ni-based bimetallic heterogeneous catalysts for energy and environmental applications, Energ. Environ. Sci. 9 (2016) 3314–3347. Y.Z. Wang, S. De, N. Yan, Rational control of nano-scale metal-catalysts for biomass conversion, Chem. Commun. (Camb.) 52 (2016) 6210–6224. Y.T. Guo, X. Chen, X. Zhang, S.J. Pu, X.T. Zhang, C.L. Yang, D.L. Li, Comparative studies on ZIF-8 and SiO2 nanoparticles as carrier for immobilized β-glucosidase, Mol. Catal. 459 (2018) 1–7. C.Y. Guo, Y.H. Zhang, X. Nan, C. Feng, Y. Guo, J.D. Wang, Efficient selective catalytic oxidation of benzylic CH bonds by ZIF-67 under eco-friendly conditions, Mol. Catal. 440 (2017) 168–174. J.H. Zhao, Z.C. Tang, F. Dong, J.Y. Zhan, Controlled porous hollow Co3O4 polyhedral nanocages derived from metal-organic frameworks (MOFs) for toluene catalytic oxidation, Mol. Catal. 463 (2019) 77–86. H.Y.H. Kim, J. Choi, A.C.K. Yip, Thermal stability of ZIF-8 under oxidative and inert environments: a practical perspective on using ZIF-8 as a catalyst support, Chem. Eng. J. 278 (2015) 293–300. R. Das, P. Pachfule, R. Banerjee, P. Poddar, Metal and metal oxide nanoparticle synthesis from metal organic frameworks (MOFs): finding the border of metal and metal oxides, Nanoscale 4 (2012) 591–595. T.N. Tran, C.H. Shin, B.J. Lee, J.S. Samdani, J.D. Park, T.H. Kang, J.S. Yu, Fe-Nfunctionalized carbon electrocatalyst derived from zeolitic imidazolate framework for oxygen reduction: Fe and NH3, treatment effects, Catal. Sci. Technol. 8 (2018) 5368–5381. Y. Li, X. Cai, S. Chen, H. Zhang, K.H.L. Zhang, J. Hong, B. Chen, D.H. Kuo, W. Wang, Highly dispersed metal carbide on ZIF-Derived Pyridinic-N-Doped carbon for CO2 enrichment and selective hydrogenation, ChemSusChem 11 (2018) 1040–1047. Y. Goto, K. Taniguchi, T. Omata, S. Otsuka-Yao-Matsuo, N. Ohashi, S. Ueda, H. Yoshikawa, Y. Yamashita, H. Oohashi, A.K. Kobayashi, Formation of Ni3C nanocrystals by thermolysis of nickel acetylacetonate in oleylamine: characterization using hard x-ray photoelectron spectroscopy, Chem. Mater. 20 (2008) 4156–4160.
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Z.-X. Li, et al. [43] H.J. Guo, H.R. Zhang, L.Q. Zhang, C. Wang, F. Peng, Q.L. Huang, L. Xiong, C. Huang, X.P. Ouyang, X.D. Chen, X.Q. Qiu, Selective hydrogenation of furfural to furfuryl alcohol over acid-activated attapulgite-supported NiCoB amorphous alloy catalyst, Ind. Eng. Chem. Res. 57 (2018) 498–511. [44] F. Pang, F. Song, Q. Zhang, Y. Tan, Y. Han, Study on the influence of oxygencontaining groups on the performance of Ni/AC catalysts in methanol vaporphase carbonylation, Chem. Eng. J. 293 (2016) 129–138. [45] X. Fan, Z. Peng, R. Ye, H. Zhou, X. Guo, M3C (M: Fe, Co, Ni) nanocrystals encased in graphene nanoribbons: an active and stable bifunctional electrocatalyst for oxygen reduction and hydrogen evolution reactions, ACS Nano 9 (2015) 7407–7418. [46] Y.P. Su, C. Chen, X.G. Zhu, Y. Zhang, W.B. Gong, H.M. Zhang, H.J. Zhao, G.Z. Wang, Carbon-embedded Ni nanocatalysts derived from MOFs by a sacrificial template method for efficient hydrogenation of furfural to tetrahydrofurfuryl alcohol, Dalton Trans. 46 (2017) 6358–6365. [47] M.H. Zhou, J. Li, K. Wang, H.H. Xia, J.M. Xu, J.C. Jiang, Selective conversion of furfural to cyclopentanone over CNT-supported Cu based catalysts: model reaction for upgrading of bio-oil, Fuel 202 (2017) 1–11. [48] C.H. Choi, S.H. Park, M.W. Chung, S.I. Woo, Easy and controlled synthesis of
nitrogen-doped carbon, Carbon 55 (2013) 98–107. [49] A.B. Ayusheev, O.P. Taran, I.A. Seryak, O.Y. Podyacheva, C. Descorme, M. Besson, L.S. Kibis, A.I. Boronin, A.I. Romanenko, Z.R. Ismagilov, V. Parmon, Ruthenium nanoparticles supported on nitrogen-doped carbonnanofibers for the catalytic wet air oxidation of phenol, Appl. Catal. B-Environ. 146 (2014) 177–185. [50] Y.F. Ma, G.Y. Xu, H. Wang, Y.X. Wang, Y. Zhang, Y. Fu, Cobalt nanocluster supported on ZrREnOx for the selective hydrogenation of biomass derived aromatic aldehydes and ketones in water, ACS Catal. 8 (2018) 1268–1277. [51] S. Sitthisa, T. Sooknoi, Y. Mac, P.B. Balbuena, D.E. Resasco, Kinetics and mechanism of hydrogenation of furfural on Cu/SiO2 catalysts, J. Catal. 277 (2011) 1–13. [52] M.X. Zhao, X.Y. Wei, M. Qu, Z.K. Li, J. Liu, J. Kong, D.D. Zhang, H.L. Yan, Z.M. Zong, A highly active solid acid for specifically catalyzing di(1-naphthyl)methane hydrocracking in cyclohexane, Fuel Process. Technol. 142 (2016) 258–263. [53] N. Sekhar, S. Arka, P. Parth, N.H. Khan, R.I. Kureshy, A.B. Panda, Hydrogenation of furfural with nickel nanoparticles stabilized on nitrogen-rich carbon core-shell and its transformations for the synthesis of γ-valerolactone in aqueous conditions, ACS Appl. Mater. Interfaces 10 (2018) 24480–24490.
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Highly selective hydrogenation of furfural and levulinic acid over Ni0.09Zn/ NC600 derived from ZIFW-8
T
Zhi-Xin Lia, Xian-Yong Weia,b,⁎, Guang-Hui Liua, Xing-Long Menga, Zheng Yanga, Shuo Niua, Di Zhanga, Hua-Shuai Gaoa, Zhi-Hao Maa, Zhi-Min Zonga a b
Key Laboratory of Coal Processing and Efficient Utilization, Ministry of Education, China University of Mining & Technology, Xuzhou, 221116, Jiangsu, China State Key Laboratory of High-efficiency Coal Utilization and Green Chemical Engineering, Ningxia University, Yinchuan, 750021, Ningxia, China
ARTICLE INFO
ABSTRACT
Keywords: Furfural Levulinic acid Selective hydrogenation Zeolitic imidazolate frameworks Ni0.09Zn/NC600
Highly selective hydrogenation of furfural and levulinic acid (LA) was studied over Ni0.09Zn/NC600 derived from zeolitic imidazolate frameworks. The existence of active Ni3ZnC0.7 particles in Ni0.09Zn/NC600 was confirmed by multiple characterizations. As a result, over Ni0.09Zn/NC600, 99.7% of furfural conversion (FC) and 100% of furan-2-ylmethanol selectivity (FMS) were achieved in isopropanol (IP) at 170 °C for 2 h, while FC and (tetrahydrofuran-2-yl)methanol (THFM) selectivity are 97.5% and 86.4% in water at 150 °C for 1 h. Over the same catalyst, LA was completely converted to γ-valerolactone in water at 95 °C for 0.5 h. The catalyst is still highly active after 6 cycles of recycling with 92.8% of FC and 100% of FMS in IP at 170 °C for 1.5 h and 90.1% of LA conversion and 100% of γ-valerolactone selectivity in water at 80 °C for 0.5 h.
1. Introduction Nowadays, the research for upgrading bio-derivates, especially bioderived furfural and levulinic acid (LA), to chemicals and fuels has received considerable attention [1,2]. Furfural obtained from corncob with a variety of reactive bonds could be selectively hydrogenated to furan-2-ylmethanol (FM), (tetrahydrofuran-2-yl)methanol (THFM), 2methylfuran (2-MF), LA, γ-valerolactone (VL), and/or cyclopentanone [3–7]. However, highly selective hydrogenation of furfural is still a problem. FM is used to produce alkyl levulinates, LA, VL, resins, biofuels, and fuel additives [7,8], while the uses of THFM include as a solvent for coating or resin and as a raw material to produce a variety of chemicals, such as pentane-1,5-diol, succinic acid, pentaerythritol, and pyranoid [9–11]. Furfural hydrogenation (FH) to FM was widely reported over either non-noble metals in liquid phase, such as Cu [12], Co [13], Ni [14], Cu-Cr [15], and Cu-Co [16], or noble metals, such as Pd [17], Pt [18], and Pd-Cu [19]. In addition, FH to THFM was intensively studied over various catalysts including Ru [10], Pd [10], Pt [11], and Ni [20]. However, since activity, selectivity, and stability of these catalysts cannot be simultaneously achieved at a low cost, there is no satisfactory catalyst for highly selective FH to FM or THFM. LA is a basic raw material to produce VL, pentane-1,4-diol, 2-methyltetrahydrofuran, and 5-nonanone [21–24]. Remarkably, VL is not
only a food additive but also a potentially ideal green solvent [25,26]. Furthermore, VL has attractive applications as a versatile intermediate for producing renewable fuels and chemicals [27–29]. However, although a variety of catalysts, such as Ni [30], Cu [31], and Ru [32], were widely used in LA hydrogenation (LAH) to VL, they have many disadvantages, such as low activity, poor selectivity, and need of relatively harsh reaction conditions. Selectively LAH to VL under mild conditions still faces challenges. With these in mind, developing a catalyst with highly selective FH and LAH is still insistent demands. Bimetallic Ni catalysts have been widely used in energy and biomass upgrading fields due to their low price and high hydrogenation activity [33,34]. In addition, carbon-based metal nanoparticles derived from newly emerging zeolitic imidazolate frameworks (ZIFWs) are extensively applied in many fields [35–39]. Notably, the metal center of ZIFWs is partially reduced as metal nanoparticles under high-temperature inert gas which is embedded in a ZIFWs-derived carbon material [38,39]. In addition, the nitrogen contained in ZIFWs is also embedded in the carbon material, which could interact with metal nanoparticles to improve the catalytic performance [40,41]. Inspired by these advances, developing a high performance catalyst derived from ZIFWs is indispensable for FH to FM or THFM and LAH to VL. In this work, we prepare a Ni0.09Zn/NC by calcining Ni0.09/ZIFW-8. The catalyst shows excellent catalytic performances for selective FH to
⁎ Corresponding author at: Key Laboratory of Coal Processing and Efficient Utilization, Ministry of Education, China University of Mining & Technology, Xuzhou, 221116, Jiangsu, China. E-mail address: [email protected] (X.-Y. Wei).
https://doi.org/10.1016/j.mcat.2019.110651 Received 25 July 2019; Received in revised form 20 September 2019; Accepted 30 September 2019 2468-8231/ © 2019 Elsevier B.V. All rights reserved.
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Fig. 1. XRD patterns of the samples.
FM in isopropanol (IP) or to THFM in water and LAH to VL in water.
2.4. Catalytic reaction
2. Experimental
A substrate (50 μL), a NixZn/NCy (50 mg), and a solvent (10 mL) are added to an 60 mL magnetically stirred autoclave. After replacing air in the autoclave with N2, a certain amount of hydrogen was filled into the autoclave. Then, the autoclave was heated to a required temperature and maintained at the temperature for an indicated period of time at 150 rpm.
2.1. Materials Furfural (99.0%), LA (99.0%), FM (99.0%), THFM (99.0%), VL (99.0%), IP, hexane, ethanol, methanol, butanol, 2-methylimidazole, Ni (NO3)2•6H2O, and Zn(NO3)2•6H2O were purchased from Aladdin Industrial Inc., Shanghai, China and used without purification. N2 and H2 used are highly pure gases.
3. Results and discussion 3.1. Catalyst characterization
2.2. Catalyst preparation
The diffraction peaks shown in Fig. 1 at 31.7°, 34.4°, 36.3°, 47.5°, 56.6°, 62.8°, 66.4°, 67.9°, and 69.7° are attributed to representative diffractions of planes (100), (002), (101), (102), (110), (103), (200), (112), and (201) of crystalline ZnO, respectively (PDF#36-1451), while the characteristic diffraction peaks located at 42.7°, 49.7°, 73.1°, and 88.5° can be attributed to representative diffraction of planes (111), (200), (220), and (311) of Ni3ZnC0.7 (PDF#28-0713), respectively. The diffraction peaks of Ni3ZnC0.7 were significantly enhanced with increasing Ni loading. Transmission electron microscopic images (Fig. S1) of NixZn/NC600 also show that the number of Ni3ZnC0.7 particles increased significantly with increasing Ni content. As observed from TG curves, Ni0.09/ZIFW-8 rapidly decomposed with raising the temperature to 320 °C under flow N2 (Fig. S2). Hence, Ni0.09Zn/NCy were prepared at 400, 500, 600, and 700 °C. The diffraction peaks of ZnO and Ni3ZnC0.7 increased with raising CT, indicating that the crystal sizes of ZnO and Ni3ZnC0.7 tend to increase at higher temperatures (Fig. 1). Ni, Zn, N, C, O, NiO, and ZnO were confirmed to exist in Ni0.09Zn/ NC600 (Table S1, Figs. 2 and S3). Peaks for Ni 2p1/2 at 870.1 eV and Ni 2p3/2 at 852.8 eV correspond to metallic Ni and peaks of Ni 2p1/2 at 871.6 and 873.0 eV and Ni 2p3/2 at 854.8, 855.8, 857.3, 858.9, and 861.2 eV could be attributed to NiO [42–44], while the peaks of Ni 2p3/ 2 at 853.6 eV suggest the existence of the carbide phase in the carbon composite [45,46] (Fig. 2). The peak at 1021.8 eV was also identified corresponding to ZnO (Fig. S3) [47]. Ni0.09Zn/NC600 contains pyridine
2.2.1. Preparation of ZIFW-8 Typically, 10.4 g Zn(NO3)2•6H2O and 7.4 g 2-methylimidazole are dissolved in 65 mL and 50 mL water, respectively [38,41]. Then, the former is quickly poured into the latter one with rapidly appearing white precipitates. After being stirred at 30 °C for 12 h, ZIFW-8 is collected by centrifugation, washed with water and ethanol sequentially, and dried at 80 °C in vacuum for 12 h. 2.2.2. Preparation of Nix/ZIFW-8 Typically, 2.47 g Ni(NO3)2•6H2O is dissolved in 70 mL ethanol. Then, 5.00 g ZIFW-8 is dispersed in the Ni(NO3)2•6H2O/ethanol solution followed by agitation at 30 °C for 12 h to obtain Ni0.09/ZIFW-8 by subsequent filtration, washing, and drying. Other Nix/ZIFW-8 species were prepared in the same way, where x represents the molar ratio of Ni to Zn (x = 0.01, 0.05, 0.09, and 0.13). 2.2.3. Preparation of NixZn/NCy Typically, Ni0.09Zn/NC600 is prepared by calcining Ni0.09/ZIFW-8 under N2 at 600 °C for 5 h. Other NixZn/NCy species were prepared in the same way, where x represents the molar ratio of Ni to Zn (x = 0.01, 0.05, 0.09, and 0.13) and y represents the calcination temperature (CT) of Nix/ZIFW-8 (y = 400, 500, 600, and 700 °C). 2.2.4. Preparation of Zn/NC and Ni/NC Zn/NC and Ni/NC were prepared by calcining ZIFW-8 and Ni-ZIFW, respectively, under N2 at 600 °C for 5 h. 2.3. Characterization techniques Each catalyst structure was characterized with a Hitachi S-3700 N scanning electron microscope combined with an energy dispersive spectrometer (EDS), a JEM-2100 microscope transmission electron microscope, an ESCALAB 250 X-ray photoelectron spectroscope, a Bruker Advance X-ray diffraction (XRD), a Nicolet Magna IR-560 Fourier transform infrared spectrometer, a TP-5000 multi-function NH3 temperature-programmed desorption (NH3-TPD) instrument, a TA SDTQ600 thermo gravimetric (TG) analyzer, and a laser ablation inductively coupled plasma mass spectrometer (LA/ICPMS).
Fig. 2. X-ray photoelectron spectrum of Ni0.09Zn/NC600. 2
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Fig. 3. Scanning electron microscopic images of ZIFW-8, Ni0.09/ZIFW-8, and Ni0.09Zn/NC600.
nitrogen and graphite nitrogen, which could increase the metal dispersion in the catalyst (Fig. S2) [48,49]. The formation of ZIFW-8 was confirmed in Fig. S4. ZIFW-8 with clearly smooth surface and particle sizes of around 1.5 μm was observed in Figs. 3 and S5. Ni0.09/ZIFW-8 was prepared by impregnating Ni with ZIFW-8 in ethanol. Its rough surface is evenly distributed with holes, facilitating better metal dispersion in the prepared Ni0.09Zn/NC600 by subsequent calcination (Figs. 3 and 4). In addition, as Fig. 3 shows, Ni0.09Zn/NC600 maintains the basic structure of Ni0.09/ZIFW-8, but its surface obviously collapses partially and becomes rougher. The uniform distribution of Ni, Zn, N, C, and O in Ni0.09Zn/NC600 shown in Fig. S6 indicates that the nitrogen element was successfully inset into Ni0.09Zn/ NC600. The uniform dispersion of Ni3ZnC0.7 particles was also observed in Fig. 4. The particle size of Ni3ZnC0.7 gradually increased with raising
CT, which is consistent with the XRD analysis (Fig. 4). The lattice spacing (0.215 nm) corresponds to the d(111) in Ni3ZnC0.7, confirming the existence of Ni3ZnC0.7 [41].
Fig. 4. Transmission electron microscopic images of the samples.
Fig. 5. Transmission electron microscopic images of Ni0.09Zn/NC600.
3.2. FH to FM over Ni0.09Zn/NC600 3.2.1. Effects of the molar ratio of Ni to Zn in NixZn/NC600, CT of Ni0.09/ ZIFW-8, and solvent on FH over Ni0.09Zn/NC600 Table S2 shows that FH did not proceed over Zn/NC, while Ni/NC led to the excessive FH, resulting in low FM selectivity (FMS). In IP, furfural was not hydrogenated over Ni0.01Zn/NC600. FM is the only product from FH over Ni0.05Zn/NC600, Ni0.09Zn/NC600, and Ni0.13Zn/ NC600, and FC increased with increasing Ni/Zn molar ratio in the catalyst, since a lot of Ni3ZnC0.7 was formed by the interaction between Ni and Zn/NC. In water, both FC and THFM selectivity (THFMS) increased with increasing Ni/Zn molar ratio up to 0.09 in NixZn/NC600, but further increase in Ni/Zn molar ratio decreased THFMS (Table S3). Similar tendancy for LA conversion (LAC) was also observed in Table S4, while VL is the only product from LAH (Fig. 5). As displayed in Fig. 6, FC increased to ca. 99% with raising the CT to 600 °C in IP. However, at higher CTs, FC dramatically dropped, perhaps due to the increase in Ni3ZnC0.7 particle size in Ni0.09Zn/NC700 (Figs. 4 and 6a). As shown in Fig. 7, relatively high FMSs were obtained in moderately polar solvents over Ni0.09Zn/NC600. FH did not proceed in hexane and is difficult in methanol and ethanol. Although FC is near 100% and
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3.2.2. Effects of reaction parameters on FH to FM over Ni0.09Zn/NC600 As Fig. 9 displays, FC increased up to almost 100% with prolonging time to 2 h, raising temperature to 170 °C, and increasing initial hydrogen pressure (IHP) to 2 MPa, while FM is the only product in FH.
Fig. 6. CT effect of Ni0.09/ZIF-8 on FH over Ni0.09Zn/NCy under 2 MPa of IHP at 170 °C for 2 h in IP.
Fig. 7. Solvent effect on FH over Ni0.09Zn/NC600 under 2 MPa of IHP at 170 °C for 2 h.
Fig. 8. NH3-TPD of Ni0.09Zn/NC600.
FMS is very low in water, more THFM was produced. This could be related to different activation capacities of active components to H2 in different polar solvents and solvent-reactant interactions could also be affected the hydrogenation activity [16,19]. In addition, tetrahydrofuran-2-carbaldehyde (THFC) was not found in all the products (Table S5). As shown in Fig. 8, Ni0.09Zn/NC600 has strong acidic sites, facilitating both the formation of H+ from H2 and furfural adsorption on Ni0.09Zn/NC600 [50,51]. The > C=O group in furfural should be more easily adsorbed, activated, and hydrogenated initiated by H+ addition to the oxygen atom in > C=O [52,53]. Therefore, Ni0.09Zn/ NC600 was used to explore FC, FMS, and THFMS in IP or water. Ni0.09Zn/NC is used to denote Ni0.09Zn/NC600 in the Figures and Tables of the Supporting Material for convenience in typesetting.
Fig. 9. FH to FM over Ni0.09Zn/NC600 in IP ((a) IHP 2 MPa, 2 h; (b) IHP 2 MPa, 170 °C (c) 170 °C, 2 h; (d) IHP 2 MPa, 170 °C, 1.5 h). 4
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abstraction from the catalyst surface, H…H transfers to the furan ring, and > C–O– bond cleavage in tetrahydrofuran ring of THFM.
3.3. FH to THFM over Ni0.09Zn/NC600 in water A high THFMS was achieved by adjusting the reaction conditions. As shown in Fig. 10a, FH at lower temperatures (70 and 90 °C) has higher FMSs up to 100%. Nevertheless, with raising temperature from 90 to 150 °C, although FC increased, FMS decreased sharply, while THFMS increased rapidly and then decreased with raising temperature to 170 °C. In addition, the selectivity of other products shows a trend of gradual increase due to gradual decomposition of THFM at high temperatures. By prolonging reaction time, THFMS first increased rapidly and then decreased from 20 to 100 min, while the corresponding FMS decreased sharply (Fig. 10b). Similarly, the selectivity of other products decreased with prolonging time. These results also support the possibility that other products were derived from THFM decomposition. The selective hydrogenation of FM to THFM over Ni0.09Zn/NC600 was confirmed and THFC was never detected (Table S5). As illustrated in Scheme 1, FH proceeds via H+ addition to the oxygen atom in > C=O of furfural, H−
3.4. The leaching and reusability of Ni0.09Zn/NC600 for FH to FM in IP As summarized in Fig. S7, FC does not increase in IP after removing Ni0.09Zn/NC600, suggesting that active sites of Ni0.09Zn/NC600 were not lost. LA/ICPMS analysis also shows that Ni or Zn leaching is negligible
Fig. 11. XRD patterns of Ni0.09Zn/NC600 after 6 times of recycle.
Fig. 10. FH over Ni0.09Zn/NC600 in water under 2 MPa of IHP.
Fig. 12. LAH to VL over Ni0.09Zn/NC600 in water ((a) IHP 2 MPa, 65 °C; (b) IHP 2 MPa, 30 min; (c) IHP 2 MPa, 80 °C, 30 min).
Scheme 1. Possible mechanisms for the selective FH over Ni0.09Zn/NC600. 5
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in the reaction solution (Table S1). As exhibited in Fig. 9d and Table S7, FC only slightly decreased and FMS remains at 92.8% over Ni0.09Zn/NC600 recycled 6 times. Ni0.09Zn/ NC600 is more stable than other catalysts reported (Table S7). XRD analysis suggests that the structure of Ni0.09Zn/NC600 remains almost no change after 6 cycles (Fig. 11).
[15] [16] [17]
3.5. LAH to VL over Ni0.09Zn/NC600
[18]
As shown in Fig. 12, LAC gradually increased with raising reaction temperature from 35 to 95 °C or prolonging reaction time from 0 to 75 min, while VL selectivity remains at 100%, indicating that Ni0.09Zn/ NC600 has excellent performance for specific LAH to VL. In addition, even after 6-times recycle, the activity of Ni0.09Zn/NC600 is still at a high level compared with reported catalysts (Table S8 and Fig. 12).
[19] [20] [21]
4. Conclusions
[22]
Ni0.09Zn/NC600 obtained by calcining Ni0.09/ZIFW-8 is highly active for selective FH to FM or THFM and LAH to VL, and still active after being recycled six times. The main products from FH over Ni0.09Zn/ NC600 are FM in IP and THFM in water.
[23] [24]
Acknowledgement
[25]
This work was supported by the Key Project of Joint Fund from the National Key Research and Development Program of China (Grant 2018YFB0604602).
[26]
Appendix A. Supplementary data
[27]
Supplementary material related to this article can be found, in the online version, at doi:https://doi.org/10.1016/j.mcat.2019.110651.
[28]
References
[29] [30]
[1] J.C. Serrano-Ruiz, J.A. Dumesic, Catalytic routes for the conversion of biomass into liquid hydrocarbon transportation fuels, Energ. Environ. Sci. 4 (2011) 83–99. [2] K. Tomishige, Y. Nakagawa, M. Tamura, Selective hydrogenolysis and hydrogenation using metal catalysts directly modified with metal oxide species, Green Chem. 19 (2017) 2876–2924. [3] S. Dutta, S. De, B. Saha, M.I. Alam, Advances in conversion of hemicellulosic biomass to furfural and upgrading to biofuels, Catal. Sci. Technol. 2 (2012) 2025–2036. [4] K. Yan, G. Wu, T. Lafleur, C. Jarvis, Production, properties and catalytic hydrogenation of furfural to fuel additives and value-added chemicals, Renew. Sust. Energ. Rev. 38 (2014) 663–676. [5] X. Li, P. Jia, T. Wang, Furfural: A Promising Platform Compound for Sustainable Production of C4 and C5 Chemicals, ACS Catal. 6 (2016) 7621–7640. [6] Y. Wang, S.Y. Sang, W. Zhu, L.J. Gao, G.M. Xiao, CuNi@C catalysts with high activity derived from metal-organic frameworks precursor for conversion of furfural to cyclopentanone, Chem. Eng. J. 299 (2016) 104–111. [7] E.A. Uslamin, N.A. Kosinov, E.A. Pidko, E.J.M. Hensen, Catalytic conversion of furanic compounds over Ga-modified ZSM-5 zeolites as a route to biomass-derived aromatics, Green Chem. 20 (2018) 3818–3827. [8] K. Yan, T. Lafleura, G.S. Wu, J.Y. Liao, C. Ceng, X.M. Xie, Highly selective production of value-added γ-valerolactone from biomass-derived levulinic acid using the robust Pd nanoparticles, Appl. Catal. A-Gen. 468 (2013) 52–58. [9] B. Pholjaroen, N. Li, Y. Huang, L. Li, A. Wang, T. Zhang, Selective hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol over vanadium modified Ir/SiO2 catalyst, Catal. Today 245 (2015) 93–99. [10] N. Merat, C. Godawa, A. Gaset, High selective production of tetrahydrofurfuryl alcohol: catalytic hydrogenation of furfural and furfuryl alcohol, J. Chem. Technol. Biot. 48 (2007) 145–159. [11] S. Bhogeswararao, D. Srinivas, Catalytic conversion of furfural to industrial chemicals over supported Pt and Pd catalysts, J. Catal. 327 (2015) 65–77. [12] C.P. Jiménez-Gómez, J.A. Cecilia, F.I. Franco-Duro, M. Pozo, R. Moreno-Tost, P. Maireles-Torres, Promotion effect of Ce or Zn oxides for improving furfuryl alcohol yield in the furfural hydrogenation using inexpensive Cu-based catalysts, Mol. Catal. 455 (2018) 121–131. [13] M. Audemar, C. Ciotonea, K. De Oliveira Vigier, S. Royer, A. Ungureanu, B. Dragoi, E. Dumitriu, F. Jerome, Selective hydrogenation of furfural to furfuryl alcohol in the presence of a recyclable Cobalt/SBA-15 catalyst, ChemSusChem 8 (2015) 1885–1891. [14] H. Jeong, C. Kim, S. Yang, H. Lee, Selective hydrogenation of furanic aldehydes
[31] [32] [33] [34] [35] [36] [37] [38] [39] [40]
[41] [42]
6
using Ni nanoparticle catalysts capped with organic molecules, J. Catal. 344 (2016) 609–615. K. Yan, A.C. Chen, Efficient hydrogenation of biomass-derived furfural and levulinic acid on the facilely synthesized noble-metal-free Cu-Cr catalyst, Energ. 58 (2013) 357–363. Y. Wang, Y.N. Miao, S. Li, L.J. Gao, G.M. Xiao, Metal-organic frameworks derived bimetallic Cu-Co catalyst for efficient and selective hydrogenation of biomass-derived furfural to furfuryl alcohol, Mol. Catal. 436 (2017) 128–137. G.M. Wang, R.L. Yao, H.Y. Xin, Y.J. Guan, P. Wu, X.H. Li, At room temperature in water: efficient hydrogenation of furfural to furfuryl alcohol with a Pt/SiC-C catalyst, RSC Adv. 8 (2018) 37243–37253. C. Nguyen-Huy, J.S. Kim, S. Yoon, E. Yang, J.H. Kwak, M.S. Lee, K. An, Supported Pd nanoparticle catalysts with high activities and selectivities in liquid-phase furfural hydrogenation, Fuel 226 (2018) 607–617. K. Fulajtárova, T. Soták, M. Hronec, I. Vávra, E. Dobrock, M. Omastová, Aqueous phase hydrogenation of furfural to furfuryl alcohol over Pd-Cu catalysts, Appl. Catal. A-Gen. 502 (2015) 78–85. L. Liu, H. Lou, M. Chen, Selective hydrogenation of furfural to tetrahydrofurfuryl alcohol over Ni/CNTs and bimetallic CuNi/CNTs catalysts, Int. J. Hydrogen Energ. 41 (2016) 14721–14731. C. Xiao, T.W. Goh, Z. Qi, S. Goes, K. Brashler, C. Perez, W. Huang, Conversion of levulinic acid to γ-Valerolactone over few-layer graphene-supported ruthenium catalysts, ACS Catal. 6 (2016) 593–599. J.L. Cui, J.J. Tan, Y.L. Zhu, F.Q. Cheng, Aqueous hydrogenation of levulinic acid to 1,4-pentanediol over Momodified Ru/AC catalyst, ChemSusChem 11 (2018) 1316–1320. J.C. Serrano-Ruiz, D. Wang, J.A. Dumesic, Catalytic upgrading of levulinic acid to 5nonanone, Green Chem. 12 (2010) 574–577. Z.B. Xie, B.F. Chen, H.R. Wu, M.Y. Liu, H.Z. Liu, J.L. Zhang, G.Y. Yang, B.X. Han, Highly efficient hydrogenation of levulinic acid into 2-methyltetrahydrofuran over Ni-Cu/Al2O3-ZrO2 bifunctional catalysts, Green Chem. 21 (2019) 606–613. D.M. Alonso, S.G. Wettstein, J.A. Dumesic, Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass, Green Chem. 15 (2013) 584–595. S. Dutta, I.K.M. Yu, D.C.W. Tsang, Y.H. Ng, Y.S. Ok, J. Sherwood, J.H. Clark, Green synthesis of gamma-valerolactone (GVL) through hydrogenation of biomass-derived levulinic acid using non-noble metal catalysts: a critical review, Chem. Eng. J. 372 (2019) 992–1006. K. Dhanalaxmi, R. Singuru, S. Mondal, L. Bai, B.M. Reddy, A. Bhaumik, O. Mondal, Magnetic nanohybrid decorated porous organic polymer:synergistic catalyst for high performance levulinic acid hydrogenation, ACS Sustain. Chem. Eng. 5 (2017) 1033–1045. J.P. Lange, R. Price, P.M. Ayoub, J. Louis, L. Petrus, L. Clarke, H. Gosselink, Valeric biofuels: a platform of cellulosic transportation fuels, Angew. Chem. Int. Ed. Engl. 49 (2010) 4479–4483. K. Yan, A. Chen, Selective hydrogenation of furfural and levulinic acid to biofuels on the ecofriendly Cu–Fe catalyst, Fuel 115 (2014) 101–108. S. Song, S.K. Yao, J.H. Cao, L. Di, G.J. Wu, N.J. Guan, L.D. Li, Heterostructured Ni/ NiO composite as a robust catalyst for the hydrogenation of levulinic acid to γvalerolactone, Appl. Catal. B-Environ. 217 (2017) 115–124. Q. Xu, X.L. Li, T. Pan, C.G. Yu, J. Deng, Q.X. Guo, Y. Fu, Supported copper catalysts for highly efficient hydrogenation of biomass-derived levulinic acid and [gamma]valerolactone, Green Chem. 18 (2016) 1287–1294. O.A. Abdelrahman, A. Heyden, J.Q. Bond, Analysis of kinetics and reaction pathways in the aqueous-phase hydrogenation of levulinic acid to form γ-Valerolactone over Ru/C, ACS Catal. 4 (2014) 1171–1181. S. De, J.G. Zhang, R. Luque, N. Yan, Ni-based bimetallic heterogeneous catalysts for energy and environmental applications, Energ. Environ. Sci. 9 (2016) 3314–3347. Y.Z. Wang, S. De, N. Yan, Rational control of nano-scale metal-catalysts for biomass conversion, Chem. Commun. (Camb.) 52 (2016) 6210–6224. Y.T. Guo, X. Chen, X. Zhang, S.J. Pu, X.T. Zhang, C.L. Yang, D.L. Li, Comparative studies on ZIF-8 and SiO2 nanoparticles as carrier for immobilized β-glucosidase, Mol. Catal. 459 (2018) 1–7. C.Y. Guo, Y.H. Zhang, X. Nan, C. Feng, Y. Guo, J.D. Wang, Efficient selective catalytic oxidation of benzylic CH bonds by ZIF-67 under eco-friendly conditions, Mol. Catal. 440 (2017) 168–174. J.H. Zhao, Z.C. Tang, F. Dong, J.Y. Zhan, Controlled porous hollow Co3O4 polyhedral nanocages derived from metal-organic frameworks (MOFs) for toluene catalytic oxidation, Mol. Catal. 463 (2019) 77–86. H.Y.H. Kim, J. Choi, A.C.K. Yip, Thermal stability of ZIF-8 under oxidative and inert environments: a practical perspective on using ZIF-8 as a catalyst support, Chem. Eng. J. 278 (2015) 293–300. R. Das, P. Pachfule, R. Banerjee, P. Poddar, Metal and metal oxide nanoparticle synthesis from metal organic frameworks (MOFs): finding the border of metal and metal oxides, Nanoscale 4 (2012) 591–595. T.N. Tran, C.H. Shin, B.J. Lee, J.S. Samdani, J.D. Park, T.H. Kang, J.S. Yu, Fe-Nfunctionalized carbon electrocatalyst derived from zeolitic imidazolate framework for oxygen reduction: Fe and NH3, treatment effects, Catal. Sci. Technol. 8 (2018) 5368–5381. Y. Li, X. Cai, S. Chen, H. Zhang, K.H.L. Zhang, J. Hong, B. Chen, D.H. Kuo, W. Wang, Highly dispersed metal carbide on ZIF-Derived Pyridinic-N-Doped carbon for CO2 enrichment and selective hydrogenation, ChemSusChem 11 (2018) 1040–1047. Y. Goto, K. Taniguchi, T. Omata, S. Otsuka-Yao-Matsuo, N. Ohashi, S. Ueda, H. Yoshikawa, Y. Yamashita, H. Oohashi, A.K. Kobayashi, Formation of Ni3C nanocrystals by thermolysis of nickel acetylacetonate in oleylamine: characterization using hard x-ray photoelectron spectroscopy, Chem. Mater. 20 (2008) 4156–4160.
Molecular Catalysis 480 (2020) 110651
Z.-X. Li, et al. [43] H.J. Guo, H.R. Zhang, L.Q. Zhang, C. Wang, F. Peng, Q.L. Huang, L. Xiong, C. Huang, X.P. Ouyang, X.D. Chen, X.Q. Qiu, Selective hydrogenation of furfural to furfuryl alcohol over acid-activated attapulgite-supported NiCoB amorphous alloy catalyst, Ind. Eng. Chem. Res. 57 (2018) 498–511. [44] F. Pang, F. Song, Q. Zhang, Y. Tan, Y. Han, Study on the influence of oxygencontaining groups on the performance of Ni/AC catalysts in methanol vaporphase carbonylation, Chem. Eng. J. 293 (2016) 129–138. [45] X. Fan, Z. Peng, R. Ye, H. Zhou, X. Guo, M3C (M: Fe, Co, Ni) nanocrystals encased in graphene nanoribbons: an active and stable bifunctional electrocatalyst for oxygen reduction and hydrogen evolution reactions, ACS Nano 9 (2015) 7407–7418. [46] Y.P. Su, C. Chen, X.G. Zhu, Y. Zhang, W.B. Gong, H.M. Zhang, H.J. Zhao, G.Z. Wang, Carbon-embedded Ni nanocatalysts derived from MOFs by a sacrificial template method for efficient hydrogenation of furfural to tetrahydrofurfuryl alcohol, Dalton Trans. 46 (2017) 6358–6365. [47] M.H. Zhou, J. Li, K. Wang, H.H. Xia, J.M. Xu, J.C. Jiang, Selective conversion of furfural to cyclopentanone over CNT-supported Cu based catalysts: model reaction for upgrading of bio-oil, Fuel 202 (2017) 1–11. [48] C.H. Choi, S.H. Park, M.W. Chung, S.I. Woo, Easy and controlled synthesis of
nitrogen-doped carbon, Carbon 55 (2013) 98–107. [49] A.B. Ayusheev, O.P. Taran, I.A. Seryak, O.Y. Podyacheva, C. Descorme, M. Besson, L.S. Kibis, A.I. Boronin, A.I. Romanenko, Z.R. Ismagilov, V. Parmon, Ruthenium nanoparticles supported on nitrogen-doped carbonnanofibers for the catalytic wet air oxidation of phenol, Appl. Catal. B-Environ. 146 (2014) 177–185. [50] Y.F. Ma, G.Y. Xu, H. Wang, Y.X. Wang, Y. Zhang, Y. Fu, Cobalt nanocluster supported on ZrREnOx for the selective hydrogenation of biomass derived aromatic aldehydes and ketones in water, ACS Catal. 8 (2018) 1268–1277. [51] S. Sitthisa, T. Sooknoi, Y. Mac, P.B. Balbuena, D.E. Resasco, Kinetics and mechanism of hydrogenation of furfural on Cu/SiO2 catalysts, J. Catal. 277 (2011) 1–13. [52] M.X. Zhao, X.Y. Wei, M. Qu, Z.K. Li, J. Liu, J. Kong, D.D. Zhang, H.L. Yan, Z.M. Zong, A highly active solid acid for specifically catalyzing di(1-naphthyl)methane hydrocracking in cyclohexane, Fuel Process. Technol. 142 (2016) 258–263. [53] N. Sekhar, S. Arka, P. Parth, N.H. Khan, R.I. Kureshy, A.B. Panda, Hydrogenation of furfural with nickel nanoparticles stabilized on nitrogen-rich carbon core-shell and its transformations for the synthesis of γ-valerolactone in aqueous conditions, ACS Appl. Mater. Interfaces 10 (2018) 24480–24490.
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