Catalytic transfer hydrogenation of bio-based furfural with NiO

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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

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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)

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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.


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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


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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

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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


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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.

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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.


Catalytic transfer hydrogenation of bio-based furfural with NiO

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