Catalytic transfer hydrogenation of bio-based furfural with NiO

5 days ago - A facile yet highly efficient catalytic system was developed for the catalytic transfer hydrogenation (CTH) of biomass-derived furfural (...
0 downloads 0 Views 1MB Size
Subscriber access provided by Kaohsiung Medical University

Article

Catalytic transfer hydrogenation of biobased furfural with NiO nanoparticles Jian He, Leonhard Schill, Song Yang, and Anders Riisager ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b04579 • Publication Date (Web): 07 Nov 2018 Downloaded from http://pubs.acs.org on November 10, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

Catalytic transfer hydrogenation of bio-based furfural with NiO nanoparticles Jian He,a,b Leonhard Schill,b Song Yang,a,* Anders Riisager b,*

a

State Key Laboratory Breeding Base of Green Pesticide & Agricultural

Bioengineering, Key Laboratory of Green Pesticide & Agricultural Bioengineering, Ministry of Education, State-Local Joint Laboratory for Comprehensive Utilization of Biomass, Center for Research & Development of Fine Chemicals, Guizhou University, Guiyang 550025, PR China. b

Centre for Catalysis and Sustainable Chemistry, Department of Chemistry,

Kemitorvet Building 207, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark.

* Corresponding Authors: E-mail: [email protected] (Anders Riisager); [email protected] (Song Yang)

1 ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Abstract A facile yet highly efficient catalytic system was developed for the catalytic transfer hydrogenation (CTH) of biomass-derived furfural (FF) to furfuryl alcohol (FAOL) over commercially available NiO nanoparticles using 2-propanol as solvent and H-donor. The catalyst system yielded 94.4% of FAOL after only 30 min of reaction at 170 °C, and a satisfactory FAOL yield of 80.9% was also attained under milder reaction conditions (150 °C, 4 h). Furthermore, the NiO catalyst proved reusable for CTH of FF several times maintaining its pristine activity after calcination in air. The catalyst effectiveness was further confirmed by performing scaled-up CTH of FF and CTH of various other aldehydes. Compared to other Ni-based catalysts reported for the hydrogenation of FF, the present system absolutely averted using H2 gas as pure NiO nanoparticles with acid-base properties did not require pre-reduction.

Keywords: Biomass; furfural; catalytic transfer hydrogenation; furfuryl alcohol; Ni-based catalyst.

2 ACS Paragon Plus Environment

Page 2 of 29

Page 3 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

Introduction Catalytic upgrading of biomass-derived platform molecules to bio-fuels and value-added chemicals is important for supplementing fossil resources to comply with the increasing global energy needs and to reduce the accumulation of greenhouse gas (CO2) in the atmosphere.1-5 Furfural (FF) is a bio-based platform molecule accessible from lignocellulosic materials (e.g., hemicellulose) via acid hydrolysis.6 However, control of reactivity and selectivity of FF to desired products is challenging due to the highly functionalized nature (i.e., C=C, C-O and C-O bonds).7 An efficient strategy to obtain control is to initially convert FF to less-reactive intermediates followed by upgrading to target products.8 In this regard, a frequently used approach is selective hydrogenation to generate furfuryl alcohol (FAOL), which is a versatile intermediate for the production of adhesives, resins and synthetic fibers.9-11 The FF-to-FAOL conversion also allow synthesis of a wider range of bio-fuels and valuable chemicals by linking FF to the downstream products of furans, such as levulinic acid and γ-valerolactone, which both are of importance in the manufacture of bio-fuels and chemicals.12-16 In the past decades, two synthetic strategies have been adopted to catalytic hydrogenation of FF to FAOL. In the first strategy, gaseous H2 is used as H-donor affording excellent hydrogenation efficiency over transition metal catalysts, preferably noble metals (e.g., Ru, Pd, Pt, Au, Rh and Re).17-22 This strategy demands the need of special facilities for transport, storage and handling of high-pressure H2, which is highly flammable and explosive if combined with air. Accordingly, this limits the general applicability of the strategy.23,24 The second strategy - catalytic transfer hydrogenation (CTH) - employ formic acid or alcohol as H-donor, and is much simpler and safer in terms of experimental facilities and operations.25,26 Specifically, the acid-free, cheap and easily accessibility of alcohol, in combination with its potential dual role as a solvent and H-donor, make utilization of alcohol as H-donor attractive.27-29 Ni-based catalysts with low-cost are attractive for hydrogenation of biomass-derived 3 ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 29

molecules, as they exhibit high activity under conditions using both gaseous H2 and alcohol as H-donor.30-35 Other catalysts with noble metals (e.g., Ru) or non-noble metals (e.g., Cu) offers also good catalytic activity in the CTH of FF,30-31,36-37 however all such as-prepared catalysts based on metallic nanoparticles are susceptible to oxidation in air, which may lead to troublesome synthesis and operation when applied. Conversely, various heterogeneous catalysts containing acid-base sites, such as Hf-Beta,38 ZrPN,39 Co3O4/MC40 and γ-Fe2O3@HAP,41 have also shown to give moderate to high FAOL yields (Table 4) associated with Meerwein-Ponndorf-Verley (MPV) reduction42 with alcohol as H-donor. In this work, commercially available NiO nanoparticles are demonstrated to efficiently catalyze the CTH of FF to FAOL with high selectivities (~95%) using 2-propanol as both of solvent and H-donor under relatively mild reaction conditions (130-170 °C). The effectiveness of NiO nanoparticles as CTH catalyst is also verified for several other aldehydes. To the best of our knowledge, the direct use of NiO as catalyst for the CTH of FF to FAOL as well as MPV reduction of aldehydes without any base additives have not been reported previously. Thus, we envision that commercial NiO nanoparticles comprise an attractive and practical useful catalyst candidate for CTH of biomass-derived FF as well as the MPV reduction of aldehydes.

Experimental Materials MgO (99

95.8

96.8

180

8

87.3

85.2

97.6

160

6

85.1

81.3

95.5

180

6

71.5

66.3

92.7

OH

OH

O

OH

OH

OH

O

5 6

Page 20 of 29

OH

OH

CH2OH

O OH 11 170 5 93.7 90.0 96.1 Reaction conditions: Substrate (2 mmol), NiO (0.08 g), 2-propanol (10 mL). 5-methylfurfural (1 mmol). c 5-hydroxymethylfurfural (1 mmol).

a

b

Conclusions In this work, CTH of FF to FAOL with a simple and non-precious metal-based NiO catalyst was successfully demonstrated with 2-propanol as both of H-donor and solvent. An almost constant and excellent FAOL selectivity (~95%) was obtained at different reaction temperature and high FF conversions of 84.6 and 98.9% was achieved at 150 or 170 °C after 4 or 0.5 h of reaction, respectively. This excellent catalytic performance was related to a relative low value of activation energy (45.1 kJ/mol). Recycling experiments with the NiO catalyst for FF conversion demonstrated a gradual decrease in catalytic activity associated to surface adsorption of organic

20 ACS Paragon Plus Environment

Page 21 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

species, but initial catalyst activity was restored by calcination in air at 300 °C. In addition, a scaled-up experiment with FF and experiments with alternative aldehydes demonstrated that the catalyst system was scalable and likely highly efficient for aldehydes in general. The present study promotes the development of low-cost, readily accessible and high efficient catalysts for the CTH of biomass-derived molecules and even for the MPV reduction of aldehydes.

ASSOCIATED CONTENT: Supporting information Pore size distributions (Figure S1) and particle size distributions (Figure S2 and Table S1) of all metal oxides nanoparticles, NH3- and CO2-TPD profiles of all catalysts (Figure S3), acid and base strength distributions of all catalysts (Table S2), the results of CTH of FF to FAOL over ZrO2 (Table S3), GC spectra of reaction mixtures (Figure S4), kinetic studies (Figure S5), color of fresh, used and regenerated catalysts (Figure S6), TPR profile of NiO (Figure S7), TPD profiles of fresh and regenerated catalyst (Figure S8), and 1H NMR spectrum of the liquid product after CTH of FF and evaporation (Figure S9).

Acknowledgement The Chinese State Scholarship (No. 201606670008) is acknowledged for supporting JH in conducting this study at the Technical University of Denmark. SY acknowledges the National Natural Science Foundation of China (No. 21576059 and 21666008), AR acknowledges the Department of Chemistry, Technical University of Denmark for support.

Reference (1) Tomishige, K.; Nakagawa, Y.; Tamura, M. Selective hydrogenolysis and hydrogenation using metal catalysts directly modified with metal oxide species. Green Chem. 2017, 19 (13), 2876-2924, DOI 10.1039/C7GC00620A. 21 ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(2) Zhu, S.; Guo, J.; Wang, X.; Wang, J.; Fan, W. Alcoholysis: A promising technology for conversion of lignocellulose and platform chemicals. ChemSusChem 2017, 10 (12), 2547-2559, DOI org/10.1002/cssc.201700597. (3) Li, H.; Yang, S.; Saravanamurugan, S.; Riisager, A. Glucose isomerization by enzymes and chemo-catalysts: status and current advances. ACS Catal. 2017, 7 (4), 3010-3029, DOI 10.1021/acscatal.6b03625. (4) Yu, I. K. M.; Tsang, D. C. W. Conversion of biomass to hydroxymethylfurfural: A review of catalytic systems and underlying mechanisms. Bioresour. Technol. 2017, 238, 716-732, DOI org/10.1016/j.biortech.2017.04.026. (5) Li, H.; Yang, S.; Riisager, A.; Pandey, A.; Sangwan, R. S.; Saravanamurugan, S.; Luque, R. Zeolite and zeotype-catalysed transformations of biofuranic compounds. Green Chem. 2016, 18 (21), 5701-5735, DOI 10.1039/C6GC02415G. (6) Shuai, L.; Luterbacher, J. Organic solvent effects in biomass conversion reactions. ChemSusChem 2016, 9 (2), 133-155, DOI org/10.1002/cssc.201501148. (7) Thompson, S. T.; Lamb, H. H. Catalysts for selective hydrogenation of furfural derived from the double complex salt [Pd(NH3)4](ReO4)2 on gamma-Al2O3. J. Catal. 2017, 350, 111-121, DOI org/10.1016/j.jcat.2017.03.019. (8) Serrano-Ruiz, J. C.; Wang, D.; Dumesic, J. A. Catalytic upgrading of levulinic acid to 5-nonanone. Green Chem. 2010, 12 (4), 574-577, DOI 10.1039/B923907C. (9) Rogers, S. M.; Catlow, C. A. R.; Chan-Thaw, C. E.; Chutia, A.; Jian, N.; Palmer, R. E.; Perdjon, M.; Thetford, A.; Dimitratos, N.; Villa, A.; Wells, P. P. Tandem siteand size-controlled Pd nanoparticles for the directed hydrogenation of furfural. ACS Catal. 2017, 7 (4), 2266-2274, DOI 10.1021/acscatal.6b03190. (10) Guigo, N.; Mija, A.; Vincent, L.; Sbirrazzuoli, N. Chemorheological analysis and model-free kinetics of acid catalysed furfuryl alcohol polymerization. Phys. Chem. Chem. Phys. 2007, 9 (39), 5359-5366, DOI 10.1039/B707950H. (11) Deka, H.; Misra, M.; Mohanty, A. Renewable resource based “all green composites” from kenaf biofiber and poly(furfuryl alcohol) bioresin. Ind. Crop Prod. 2013, 41, 94-101, DOI org/10.1016/j.indcrop.2012.03.037. (12) Antunes, M. M.; Lima, S.; Neves, P.; Magalhães, A. L.; Fazio, E.; Neri, F.; 22 ACS Paragon Plus Environment

Page 22 of 29

Page 23 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

Pereira, M. T.; Silva, A. F.; Silva, C. M.; Rocha, S. M.; Pillinger, M.; Urakawa, A.; Valente, A. A. Integrated reduction and acid-catalysed conversion of furfural in alcohol medium using Zr,Al-containing ordered micro/mesoporous silicates. Appl.Catal. B: Environ. 2016, 182, 485-503, DOI org/10.1016/j.apcatb.2015.09.053. (13) Bui, L.; Luo, H.; Gunther, W. R.; Román-Leshkov, Y. Domino reaction catalyzed by zeolites with Brønsted and Lewis acid sites for the production of γ-valerolactone from furfural. Angew. Chem. Int. Ed. 2013, 125 (31), 8180-8183, DOI org/10.1002/ange.201302575. (14) Alonso, D. M.; Wettstein, S. G.; Dumesic, J. A. Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass. Green Chem. 2013, 15, 584-595, DOI 10.1039/C3GC37065H. (15) Pileidis, F. D.; Titirici, M. Levulinic acid biorefineries: new challenges for efficient utilization of biomass. ChemSusChem 2016, 9 (6), 562-582, DOI org/10.1002/cssc.201501405. [16] Yan, K.; Yang, Y.; Chai, J.; Lu, Y. Catalytic reactions of gamma-valerolactone: a platform to fuels and value-added chemicals. Appl. Catal. B: Environ. 2015, 179, 292-304, DOI org/10.1016/j.apcatb.2015.04.030. (17) Musci, J. J.; Merlo, A. B.; Casella, M. L. Aqueous phase hydrogenation of furfural using carbon-supported Ru and RuSn catalysts. Catal. Today 2017, 296, 43-50, DOI org/10.1016/j.cattod.2017.04.063. (18) Fulajtárova, K.; Soták, T.; Hronec, M.; Vávra, I.; Dobročka, E.; Omastová, M. Aqueous phase hydrogenation of furfural to furfuryl alcohol over Pd-Cu catalysts. Appl. Catal. A: Gen. 2015, 502, 78-85, DOI org/10.1016/j.apcata.2015.05.031. (19) Dohade, M. G.; Dhepe, P. L. Efficient hydrogenation of concentrated aqueous furfural solutions into furfuryl alcohol under ambient conditions in presence of PtCo bimetallic

catalyst.

Green

Chem.

2017,

19

(4),

1144-1154,

DOI

10.1039/C6GC03143A. (20) Li, M.; Hao, Y.; Cárdenas-Lizana, F.; Keane, M. A. Selective production of furfuryl alcohol via gas phase hydrogenation of furfural over Au/Al2O3. Catal. Commun. 2015, 69, 119-122, DOI org/10.1016/j.catcom.2015.06.007. 23 ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 29

(21) Castelbou, L. J.; Szeto, K. C.; Barakat, W.; Merle, N.; Godard, C.; Taoufik, M.; Claver, C. A new approach for the preparation of well-defined Rh and Pt nanoparticles

stabilized

by

phosphine-functionalized

silica

for

selective

hydrogenation reactions. Chem. Commun. 2017, 53 (22), 3261-3264, DOI 10.1039/C6CC10338C. (22) Thompson, S. T.; Lamb, H. H. Palladium-rhenium catalysts for selective hydrogenation of furfural: evidence for an optimum surface composition. ACS Catal. 2016, 6 (11), 7438-7447, DOI 10.1021/acscatal.6b01398. (23) Tang, X.; Chen, H.; Hu, L.; Hao, W.; Sun, Y.; Zeng, X.; Lin, L.; Liu, S. Conversion of biomass to γ-valerolactone by catalytic transfer hydrogenation of ethyl levulinate over metal hydroxides. Appl. Catal. B: Environ. 2014, 147, 827-834, DOI org/10.1016/j.apcatb.2013.10.021. (24) Biradar, N. S.; Hengne, A. M.; Sakate, S. S.; Swami, R. K.; Rode, C. V. Single pot transfer hydrogenation and aldolization of furfural over metal oxide catalysts. Catal. Lett. 2016, 146 (8), 1611-1619, DOI 10.1007/s10562-016-1786-6. (25) Osatiashtiani, A.; Lee, A. F.; Wilson, K. Recent advances in the production of γ-valerolactone from biomass-derived feedstocks via heterogeneous catalytic transfer hydrogenation. J. Chem. Technol. Biotechnol. 2017, 92 (6), 1125-1135, DOI org/10.1002/jctb.5213. (26) Gilkey, M. J.; Xu, B. Heterogeneous catalytic transfer hydrogenation as an effective pathway in biomass upgrading. ACS Catal. 2016, 6 (3), 1420-1436, DOI 10.1021/acscatal.5b02171. (27) Scholz, D.; Aellig, C.; Mondelli, C.; Pérez-Ramírez, J. Continuous transfer hydrogenation of sugars to alditols with bioderived donors over Cu-Ni-Al catalysts. ChemCatChem 2015, 7 (10), 1551-1558, DOI org/10.1002/cctc.201403005. (28) He, J.; Li, H.; Riisager, A.; Yang, S. Catalytic transfer hydrogenation of furfural to furfuryl alcohol with recyclable Al-Zr@Fe mixed oxides. ChemCatChem 2018, 10 (2), 430-438, DOI org/10.1002/cctc.201701266. (29) Aellig, C.; Jenny, F.; Scholz, D.; Wolf, P.; Giovinazzo, I.; Kollhoff, F.; Hermans, I. Combined 1,4-butanediol lactonization and transfer hydrogenation/hydrogenolysis 24 ACS Paragon Plus Environment

Page 25 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

of furfural derivatives under continuous flow conditions. Catal. Sci. Technol. 2014, 4 (8), 2326-2331, DOI 10.1039/C4CY00213J. (30) Khromova, S. A.; Bykova, M. V.; Bulavchenko, O. A.; Ermakov, D. Y.; Saraev, A. A.; Kaichev, V. V.; Venderbosch, R. H.; Yakovlev, V. A. Furfural hydrogenation to furfuryl alcohol over bimetallic Ni-Cu sol-gel catalyst: a model reaction for conversion of oxygenates in pyrolysis liquids. Top. Catal. 2016, 59 (15-16), 1413-1423, DOI org/10.1007/s11244-016-0649-0. (31) Kannapu, H. P. R.; Mullen, C. A.; Elkasabi, Y.; Boateng, A. A. Catalytic transfer hydrogenation for stabilization of bio-oil oxygenates: reduction of p-cresol and furfural over bimetallic Ni-Cu catalysts using isopropanol. Fuel Process. Technol. 2015, 137, 220-228, DOI org/10.1016/j.fuproc.2015.04.023. (32) Jeong, H.; Kim, C.; Yang, S.; Lee, H. Selective hydrogenation of furanic aldehydes using Ni nanoparticle catalysts capped with organic molecules. J. Catal. 2016, 344, 609-615, DOI org/10.1016/j.jcat.2016.11.002. (33) Seemala, B.; Cai, C. M.; Wyman, C. E.; Christopher, P. Support induced control of surface composition in Cu-Ni/TiO2 catalysts enables high yield co-conversion of HMF and furfural to methylated furans. ACS Catal. 2017, 7 (6), 4070-4082, DOI 10.1021/acscatal.7b01095. [34] Chen, B.; Li, F.; Huang, Z.; Yuan, G. Tuning catalytic selectivity of liquid-phase hydrogenation of furfural via synergistic effects of supported bimetallic catalysts. Appl. Catal. A: Gen. 2015, 500, 23-29, DOI org/10.1016/j.apcata.2015.05.006. (35) Gong, W.; Chen, C.; Zhang, H.; Zhang, Y.; Zhang, Y.; Wang, G.; Zhao, H. Highly selective liquid-phase hydrogenation of furfural over N-doped carbon supported metallic nickel catalyst under mild conditions. Mol. Catal. 2017, 429, 51-59, DOI org/10.1016/j.molcata.2016.12.004. (36) Panagiotopoulou, P.; Martin, N.; Vlachos, D. G. Liquid-phase catalytic transfer hydrogenation

of

furfural

over

homogeneous

Lewis

acid-Ru/C

catalysts.

ChemSusChem 2015, 8 (12), 2046-2054, DOI org/10.1002/cssc.201500212. (37) Zhang, J.; Chen, J. Selective transfer hydrogenation of biomass-based furfural and 5-hydroxymethylfurfural over hydrotalcite-derived copper catalysts using 25 ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 29

methanol as a hydrogen donor. ACS Sustain. Chem. Eng. 2017, 5 (7), 5982-5993, DOI 10.1021/acssuschemeng.7b00778. (38) Koehle, M.; Lobo, R. F. Lewis acidic zeolite Beta catalyst for the Meerwein-Ponndorf-Verley reduction of furfural. Catal. Sci. Technol. 2016, 6 (9), 3018-3026, DOI 10.1039/C5CY01501D. (39) Li, H.; He, J.; Riisager, A.; Saravanamurugan, S.; Song, B.; Yang, S. Acid-base bifunctional zirconium N-alkyltriphosphate nanohybrid for hydrogen transfer of biomass-derived

carboxides.

ACS

Catal.

2016,

6

(11),

7722-7727,

DOI

10.1021/acscatal.6b02431. (40) Wang, G.; Deng, X.; Gu, D.; Chen, K.; Tüysüz, H.; Spliethoff, B.; Bongard, H.; Weidenthaler, C.; Schmidt, W.; Schüth, F. Co3O4 nanoparticles supported on mesoporous carbon for selective transfer hydrogenation of α,β-unsaturated aldehydes. Angew.

Chem.

Int.

Ed.

2016,

128

(37),

11267-11271,

DOI

org/10.1002/ange.201604673. (41) Wang, F.; Zhang, Z. Catalytic transfer hydrogenation of furfural into furfuryl alcohol over magnetic γ-Fe2O3@HAP catalyst. ACS Sustain. Chem. Eng. 2017, 5 (1), 942-947, DOI 10.1021/acssuschemeng.6b02272. [42] Gonell, F.; Boronat, M.; Corma, A. Structure-reactivity relationship in isolated Zr sites present in Zr-zeolite and ZrO2 for the Meerwein-Ponndorf-Verley reaction. Catal. Sci. Technol. 2017, 7 (13), 2865-2873, DOI 10.1039/C7CY00567A. (43) He, J.; Li, H.; Liu, Y.; Zhao, W.; Yang, T.; Xue, W.; Yang, S. Catalytic transfer hydrogenation of ethyl levulinate into γ-valerolactone over mesoporous Zr/B mixed oxides. J. Ind. Eng. Chem. 2016, 43, 133-141, DOI org/10.1016/j.jiec.2016.07.059. (44)

Sushkevich,

V.

L.;

Ivanova,

I.

I.;

Tolborg,

S.;

Taarning,

E.

Meerwein-Ponndorf-Verley-Oppenauer reaction of crotonaldehyde with ethanol over Zr-containing

catalysts.

J.

Catal.

2014,

316,

121-129,

DOI

org/10.1016/j.jcat.2014.04.019. (45) Zhang, J.; Dong, K.; Luo, W.; Guan, H. Selective transfer hydrogenation of furfural into furfuryl alcohol on Zr-containing catalysts using lower alcohols as hydrogen

donors.

ACS

Omega

2018,

3

26 ACS Paragon Plus Environment

(6),

6206-6216,

DOI

Page 27 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

10.1021/acsomega.8b00138. (46) Xue, Z.; Jiang, J.; Li, G.; Zhao, W.; Wang, J.; Mu, T. Zirconium-cyanuric acid coordination polymer: highly efficient catalyst for conversion of levulinic acid to γ-valerolactone.

Catal.

Sci.

Technol.

2016,

6

(14),

5374-5379,

DOI

10.1039/C5CY02215K. (47) Li, F.; France, L. J.; Cai, Z.; Li, Y.; Liu, S.; Lou, H.; Long, J.; Li, X. Catalytic transfer hydrogenation of butyl levulinate to γ-valerolactone over zirconium phosphates with adjustable Lewis and Brønsted acid sites. Appl. Catal. B: Environ. 2017, 214, 67-77, DOI org/10.1016/j.apcatb.2017.05.013. (48) Gross, B. H.; Mebane, R. C.; Armstrong, D. L. Transfer hydrogenolysis of aromatic alcohols using Raney catalysts and 2-propanol. Appl. Catal. A: Gen. 2001, 219 (1-2), 281-289, DOI org/10.1016/S0926-860X(01)00700-1. (49) Gao, Z.; Yang, L.; Fan, G.; Li, F. Promotional role of surface defects on carbon-supported Ru-based catalysts in transfer hydrogenation of furfural. ChemCatChem 2016, 8 (24), 3769-3779, DOI org/10.1002/cctc.201601070. (50) Li, J.; Liu, J.; Zhou, H.; Fu, Y. Catalytic transfer hydrogenation of furfural to furfuryl alcohol over nitrogen-doped carbon-supported iron catalysts. ChemSusChem 2016, 9 (11), 1339-1347, DOI org/10.1002/cssc.201600089. (51)

Scholz,

D.;

Aellig,

hydrogenation/hydrogenolysis 5-(hydroxymethyl)furfural.

for

C.;

Hermans,

reductive

ChemSusChem

I.

Catalytic

upgrading

2014,

7

(1),

of

transfer

furfural 268-275,

and DOI

org/10.1002/cssc.201300774. (52) Kaviyarasu, K.; Manikandan, E.; Manikandan, J.; Jayachandran, M.; Ladchumananandasiivam, R.; Gomes, U. U. D.; Maaza, M. Synthesis and characterization studies of NiO nanorods for enhancing solar cell efficiency using photon upconversion materials. Ceramic. Int. 2016, 42 (7), 8385-8394, DOI org/10.1016/j.ceramint.2016.02.054. (53) Thema, F. T.; Manikandan, E.; Gurib-Fakim, A.; Maaza, M. Single phase bunsenite NiO nanoparticles green synthesis by agathosma betulina natural extract. J. Alloy. Compd. 2016, 657, 655-661, DOI org/10.1016/j.jallcom.2015.09.227. 27 ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 29

(54) Contarini, S.; Michalik, J.; Narayana, M.; Kevan, L. Correlated X-ray photoelectron and electron spin resonance spectroscopic investigations of the reducibility of Nickel(II) in Na-X and Ca-X zeolites. J. Phys. Chem. 1986, 90 (19), 4586-4590, DOI 10.1021/j100410a023. (55) Chen, P.; Zhang, H.; Lin, G.; Tsai, K. Development of coking-resistant Ni-based catalyst for partial oxidation and CO2-reforming of methane to syngas. Appl. Catal. A: Gen. 1998, 166 (2), 343-350, DOI org/10.1016/S0926-860X(97)00291-3. (56) Peck, M. A.; Langell, M. A. Comparison of nanoscaled and bulk NiO structural and environmental characteristics by XRD, XAFS, and XPS. Chem. Mater. 2012, 24 (23), 4483-4490, DOI 10.1021/cm300739y. (57) Song, S.; Yao, S.; Cao, J.; Di, L.; Wu, G.; Guan, N.; Li, L. Heterostructured Ni/NiO composite as a robust catalyst for the hydrogenation of levulinic acid to γ-valerolactone.

Appl.

Catal.

B:

Environ.

2017,

org/10.1016/j.apcatb.2017.05.073.

28 ACS Paragon Plus Environment

217,

115-124,

DOI

Page 29 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

For Table of Contents Use Only

NiO nanoparticles are shown to be highly efficient and durable catalyst for transfer hydrogenation of biomass-derived furfural to furfuryl alcohol in 2-propanol without pre-reduction and base additives.

29 ACS Paragon Plus Environment