Porous Hafnium Phosphonate: Novel Heterogeneous Catalyst for

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Porous Hafnium Phosphonate: Novel Heterogeneous Catalyst for Conversion of Levulinic Acid and Esters into #-Valerolactone Chao Xie, Jinliang Song, Baowen Zhou, Jiayin Hu, Zhanrong Zhang, Pei Zhang, Zhiwei Jiang, and Buxing Han ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.6b02230 • Publication Date (Web): 14 Oct 2016 Downloaded from http://pubs.acs.org on October 17, 2016

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ACS Sustainable Chemistry & Engineering

Porous Hafnium Phosphonate: Novel Heterogeneous Catalyst for Conversion of Levulinic Acid and Esters into γ-Valerolactone

Chao Xie,†,‡ Jinliang Song,*,† Baowen Zhou,†,‡ Jiayin Hu,†,‡ Zhanrong Zhang,† Pei Zhang,† Zhiwei Jiang,† and Buxing Han*,†,‡ †

Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, No.

2 Zhongguancun North First Street, Haidian District, Beijing 100190, P.R.China ‡

University of Chinese Academy of Sciences, 19A Yuquan Road, Shijingshan District, Beijing 100049,

P.R.China

ABSTRACT: Catalytic transfer hydrogenation (CTH) of levulinic acid (LA) and its esters to produce γ-valerolactone (GVL) is an important route for biomass transformation. Development of efficient and heterogeneous catalysts for the GVL production via CTH reaction of LA and its esters has attracted much attention. In this work, a new hafnium (Hf)-containing organic-inorganic hybrid catalyst (Hf-ATMP) was prepared by the reaction of HfCl4 and amino tri(methylene phosphonic acid) and was used to catalyze the CTH reaction of LA and its esters to produce GVL using isopropanol as the hydrogen source. It was found that the prepared Hf-ATMP could catalyze the CTH reaction to provide satisfactory GVL yield, and the effects of reaction temperature, reaction time, and the amount of the catalyst on the reaction were studied in detail. Meanwhile, the Hf-ATMP could be reused at least five times without notable decrease in activity and selectivity. Systematic studies indicated that the acidity of Hf, the basicity of the phosphate groups, and the porosity of the prepared catalyst were the main reasons for the catalytic performance of Hf-ATMP in the CTH reaction of LA and its esters.

KEYWORDS: γ-Valerolactone, levulinic acid and esters, catalytic transfer hydrogenation, organic-inorganic hybrid catalyst, biomass transformation

ACS Paragon Plus Environment


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INTRODUCTION Transformation of renewable lignocellulose into value-added chemicals, fuels and materials has attracted much attention due to the gradual depletion of fossil-based resources.1-3 Up to now, diverse valuable chemicals can be synthesized

from

lignocellulose,

including

various

alcohols,4,5

short

chain

hydrocarbons,6,7

5-hydroxymethylfurfural,8,9 organic acids,10,11 and γ-valerolactone (GVL),12,13 etc. Among these compounds, GVL has been recognized as a versatile platform chemical, which can be used as green solvent, fuel additive, food additive, and a precursor for more valuable chemicals.14-18 GVL can be produced from the hydrogenation of cellulose and hemicellulose-derived levulinic acid (LA) and its esters over various metal catalysts, such as Pd,19 Ru,20 Pt,21 Ni,22 Co,23 Mo,24 Ir25 and Cu.26 However, these H2 approaches suffer from high H2 pressure, and low catalyst stability and reactivity of non-noble metal catalysts, etc. In recent years, as an attractive alternative to H2 process, catalytic transfer hydrogenation (CTH) reaction has been considered as an efficient way to synthesize GVL from LA and its esters by using formic acid or alcohols as the hydrogen source. As an alternative choice, formic acid has been used in CTH reaction of LA and its esters catalyzed by Au27 and Ru 12 catalysts, but the harsh reaction conditions, and the corrosiveness of formic acid have limited the application of the formic acid process in the production of GVL. In contrast, using alcohols as the hydrogen source provided a more promising approach for CTH reaction of LA and its esters to produce GVL. Up to now, several catalysts have been explored for GVL production via CTH reaction of LA and its esters in the presence of different alcohols. For example, Chia and Dumesic reported that ZrO2 could catalyze the CTH of LA and its esters with secondary alcohols.28 Meanwhile, Zr-Beta zeolite has been proved to be an efficient catalyst for GVL production from CTH of LA and its esters.29 Furthermore, the CTH of ethyl levulinate (EL) could be carried out over metal hydroxidesin various alcohols30 or ZrO2 in supercritical ethanol.31 In addition, homogeneous Ru complexes32 and RANEY® Ni33 could also catalyze the CTH of LA and its esters for the formation of GVL. Very recently, earth-abundant metal nanoparticles have been used as efficient catalyst for the conversion of LA into GVL using ethanol as the hydrogen source in the presence of KOH.34 In our previous works, a porous Zr-containing catalyst with phenate groups and a porous Zr-phytic acid hybrid catalyst have been prepared to catalyze the CTH of LA and its esters to GVL efficiently.35, 36 Development of novel heterogeneous catalysts for CTH reaction of LA and its esters to produce GVL is still highly desirable, although many catalysts have been reported. In this work, we synthesized a new porous


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and heterogeneous organic-inorganic hybrid Hf-containing catalyst (termed Hf-ATMP hereafter) based on HfCl4 and amino tri(methylene phosphonic acid) (ATMP, Scheme 1) in N,N-dimethylformamide (DMF) for the CTH reaction of LA and its esters to produce GVL using isopropanol as the hydrogen source. It was found that the prepared Hf-ATMP could catalyze the CTH reaction to provide satisfactory GVL yield, indicating that Hf could be used as the catalytic active centre for the CTH reaction. As far as we know, this is the first report on the application of Hf-containing organic-inorganic hybrid catalysts (Hf-ATMP) for the CTH reaction of LA and its esters to produce GVL.

Scheme 1. The structures of (a) amino tri(methylene phosphonicacid) and (b) 1,2-ethylenediphosphonic acid (EDPA).

EXPERIMENTAL SECTION Materials Ethyl levulinate (98%), methyl levulinate (99%), butyl levulinate (98%), levulinic acid (99%) and γ-valerolactone (98%) were purchased from J&K Scientific Ltd. Amino tri(methylene phosphonic acid) (ATMP, 50 wt% in water)

was

obtained

from

TCI.

Hafnium

oxide

was

provided

by

Adamas.

HfCl4

(AR)

and

1,2-ethylenediphosphonic acid (97%, EDPA) were obtained from Alfa. All other chemicals were provided by Beijing Chemical Reagent Company and all chemicals were used directly without any further purification

Preparation of Hf-ATMP HfCl4 (7.5 mmol) and ATMP (5 mmol) were dissolved in DMF (250 mL), respectively. Then, the solution of ATMP was added dropwise into HfCl4 solution in 2 h. After that, the mixture was continuously stirred for 12 h at room temperature, then aged at 80 oC under static conditions for 3 h. The white precipitate was separated by filtration, and washed with DMF, ethanol, and ethyl ether, respectively. Finally, the obtained Hf-ATMP was dried at 80

o

C under vacuum for 12 h. Anal. Found: 46.83% Hf, 17.02% P, 6.59% C. Calcd. for



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Hf3N2P6C6O18H12 (1121.48): 47.74% Hf, 16.57% P, 6.43% C. Meanwhile, other catalysts with different metal ions (Cu, Zn, Al and Cr) and different ligand (EDPA) were synthesized using a similar route for Hf-ATMP.

Catalyst characterization The scanning electron microscopy (SEM) measurements were performed on a Hitachi S-4800 Scanning Electron Microscope operated at 15 kV. The transmission electron microscopy (TEM) images were obtained using a TEM JeoL-1011 with an accelerating voltage of 120 kV. Powder X-ray diffraction (XRD) patterns were collected on a Rigaku D/max-2500 X-ray diffractometer using Cu-Kαradiation (λ=0.154 nm). FT-IR spectra were recorded using a Bruker Tensor 27 spectrometer and the samples were prepared by the KBr pellet method. The N2 adsorption-desorption isotherm was determined using the Micromeritics ASAP 2020msystem. X-ray photoelectron spectroscopy (XPS) measurements were carried out on a ESCAL Lab 220i-XL specrometer. Temperature-programmed desorptions of carbon dioxide (CO2-TPD) and ammonia (NH3-TPD) were performed on Micromeritics’ AutoChem 2950 HP Chemisorption Analyzer. The contents of Hf and P in Hf-ATMP and the concentration of Hf in the reaction solution were determined by ICP-AES (VISTA-MPX). The content of C and H was obtained from elemental analysis by using the FLASH EA1112 analyzer.

Catalytic reaction In a typical experiment, reactant (LA or its esters, 1 mmol), isopropanol (4 ml) and the catalyst (200 mg) were added into a stainless reactor of 22 ml. After the reactor was sealed, the reaction mixture was stirred at a desired temperature for the desired time. When the reaction was completed, the products were analyzed quantitatively by gas chromatography (GC, Agilent 6820) equipped with flame ionization detector (FID) and using ethylbenzene as the internal standard (0.05 g, and the calibration curves were provided in Figure S1). Identification of the products was done by GC-MS (Shimadzu QP2010).

Reusability of the prepared Hf-ATMP To examine the reusability of the Hf-ATMP, the catalyst was recovered by centrifugation, and washed with ethyl ether (5×10 mL). After dried under vacuum at 80 oC for 12 h, the recovered catalyst was reused for the next cycle.


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RESULTS AND DISCUSSION Catalyst characterization Hf-ATMP was prepared according to the procedure discussed in the Experimental section. The prepared Hf-ATMP was characterized by ICP-AES, X-ray diffraction (XRD), N2 adsorption-desorption examination, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). ICP analysis showed that the Hf/P molar ratio in Hf-ATMP was about 1:2, which indicated one Hf4+ can coordinate with two phosphate groups. Due to the coordination ability of all the three phosphate groups in a ATMP and the steric hindrance, the most possible connectivity pattern between Hf4+ and ATMP was shown in Scheme S1 and the network of Hf-ATMP was mainly generated through this connectivity pattern. However, XRD pattern (Figure 1a) indicated that the Hf-ATMP had low crystallinity or was poorly ordered. Thus, it can be deduced that there were many defects or irregular connectivity in the Hf-ATMP. Meanwhile, the morphology of the catalyst from SEM and TEM demonstrated that the Hf-ATMP had no uniform shape (Figures 1c and 1d). In addition, the N2 adsorption-desorption isotherm indicated that the obtained Hf-ATMP was porous, and the surface area, pore volume, and average pore diameter were 222.6 m2g-1, 0.25 cm3g-1, and 16.7 nm, respectively. The low crystallinity (Figure 1a) and porous structure (Figure 1b) suggested that Hf-ATMP could be used as a good catalyst. For comparison, other metal (Cu, Zn, Al and Cr)-ATMP catalysts and other ligand catalyst Hf-EDPA were also prepared with similar textural and structural properties (Figure S2-S4 and Table S1).

Figure 1. Powder XRD pattern (a), N2 adsorption-desorption isotherm (b), TEM image (c) and SEM image (d) of Hf-ATMP



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Catalytic activity of various catalysts for the CTH of EL Firstly, we chose ethyl levulinate (EL) as the model reactant to study the performance of various catalysts for the synthesis of GVL from CTH reaction, and the results were shown in Table 1. It was found that there was no reaction happened without any catalysts (Table 1, entry 1). Among the synthesized ATMP-based catalysts, the Hf-ATMP showed the highest activity for the reaction with a EL conversion of 95% and a GVL yield of 86% at 150 oC with a reaction time of 4 h (Table 1, entry 2). However, Cu-ATMP (Table 1, entry 3), Zn-ATMP (Table 1, entry 4), Al-ATMP (Table 1, entry 5), and Cr-ATMP (Table 1, entry 6) were not active for the CTH reaction of EL to form GVL with some EL converted to isopropyl levulinate through the transesterification of EL and isopropanol. In addition, some other Hf-based catalysts were also used to catalyze the CTH of EL. The commercial HfO2 showed lower activity with a GVL yield of 35% (Table 1, entry 7), while the Hf-EDPA showed a higher GVL yield up to 74%. These results indicated that Hf-containing materials could be used as the catalysts for the CTH of EL to GVL, and the synthesized Hf-ATMP was a superior catalyst for CTH of EL. The reasons for the high performance of the prepared Hf-ATMP would be discussed in detail below.

Table 1. The performance of various catalysts for the CTH reaction of EL to produce GVL.a

a

Entry

Catalyst

Conversion (%)b

Yield (%)b

Selectivity (%)

1

None

0

0

--

2

Hf-ATMP

95 (±2.1)

86 (±1.6)

91

3

Cu-ATMP

10 (±1.3)

99

97 (±1.2)

97

3

Butyl levulinate

7

88 (±1.8)

80 (±2.1)

91

4

Levulinic acid

4

>99

98 (±0.7)

98

a

Reaction conditions: 1 mmol substrate; 200 mg Hf-ATMP (52 mol% Hf); 4ml isopropanol; reaction temperature 150

o

C. bThe other products were mainly isopropyl levulinate obtained by transesterification or esterification, and the data

in parentheses are the standard deviations (%).

Reasons for the higher catalytic activity of Hf-ATMP As discussed above, Hf-ATMP showed much better performance than HfO2, which could be caused by their different acidity, basicity, and structures. Firstly, Hf element was the catalytic centre for the CTH reaction of EL. The reaction activity could be affected by the Lewis acidity of Hf. Therefore, the local environment of Hf species in Hf-ATMP and HfO2 was examined by XPS. As shown in Figure 7a, the binding energy values of Hf 4d in Hf-ATMP were higher than those of HfO2, indicating higher positive charge on Hf atoms in the Hf-ATMP, which resulted in stronger Lewis acidity.36,37 We also examined the acidity of Hf-ATMP and HfO2 by NH3-TPD method (Figure 7b), and the results suggested that Hf-ATMP had higher acidity than HfO2, which was consistent with the results from the


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XPS examination. The higher Lewis acidity of Hf-ATMP was helpful for activating the carbonyl groups in EL, and thus promoted the CTH reaction. Secondly, the basicity of the catalysts also had impact on the catalytic activity. We examined the basicity of Hf-ATMP and HfO2 by CO2-TPD method. The results in Figure 7c indicated that the prepared Hf-ATMP had higher basicity than HfO2. In our previous work,36 we had proved that the phosphate groups could increase the basicity of the catalysts. Therefore, the basicity of the synthesized Hf-ATMP was higher because of the existence of phosphate groups in the structure of ATMP, and thus enhanced the catalytic activity for the CTH reaction of EL to produce GVL by the increase of the dissociation of hydroxyl groups in isopropanol activated by basic sites (O2-) with the aid of Lewis acidic sites (Hf4+).35,36 Additionally, Hf-EDPA (without amino structure, Scheme 1) showed lower catalytic activity (Table 1, entry 8) than Hf-ATMP (with amino structure, Table 1, entry 2) because Hf-ATMP had higher basicity than Hf-EDPA as detected by CO2-TPD method (Figure 7c and Figure S5), which may be caused by the existence of amino structure in Hf-ATMP. The interaction between amino groups (as basic sites) and the hydroxyl groups could also activate the dissociation of isopropanol to corresponding alkoxide and proton, which was beneficial for the CTH reaction. Thirdly, the catalyst structure could also influence the catalytic activity of Hf-ATMP and HfO2. As examined by XRD, the prepared Hf-ATMP was amorphous with a very low crystallinity. In contrast, HfO2 showed better crystallinity (Figure 7d). The lower crystallinity of Hf-ATMP could be beneficial for the reactants to be in contact with the acid center (Hf) of the catalyst. Meanwhile, as detected by N2 adsorption-desorption, Hf-ATMP had a higher BET surface area, larger pore diameter, and larger pore volume than HfO2, which was helpful to increase the diffusion of reactants to the activity center (Hf) in Hf-ATMP (Table S1). Therefore, the lower crystallinity and the better textural properties caused Hf-ATMP had a higher catalytic activity.



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Figure 7. XPS spectra of Hf 4d (a), NH3-TPD (b), CO2-TPD (c), and XRD patterns (d) for Hf-ATMP and HfO2.

Mechanism Based on the experimental results and some reported knowledge,28-31,35,36 we proposed a possible reaction mechanism for the CTH reaction of LA and its esters to GVL over Hf-ATMP (Figure 8). In a first step, isopropanol interacted with the acid-base sites (Hf4+-O2-) or the amino groups on the Hf-ATMP, and dissociated to the corresponding alkoxide and proton. At the same time, the carbonyl groups in LA and its esters was activated by Hf4+-O2-. Then, the activated carbonyl group interacted with the nearby activated isopropanol to form a six-link intermediate, and 4-hydroxypentanoate or its ester could be formed by hydrogen transfer. Finally, GVL could be obtained from 4-hydroxypentanoate through intramolecular esterification or transesterification.


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Figure 8. Possible mechanism for CTH reaction of LA and its esters to produce GVL catalyzed by Hf-ATMP.

CONCLUSIONS In summary, we designed a novel heterogeneous Hf-containing organic-inorganic hybrid catalyst, denoted as Hf-ATMP, which could be used as the heterogeneous catalyst for the CTH reaction of LA and its esters to produce GVL in the presence of isopropanol as the hydrogen source. It was found that the prepared Hf-ATMP showed better performance for the CTH reaction than HfO2. Meanwhile, the Hf-ATMP could be reused at least five times without decrease in activity and selectivity. Systematic studies indicated that the acidity of Hf, the basicity of the phosphate groups, and the porosity of the prepared catalyst were the main reasons for the catalytic performance of Hf-ATMP in the CTH reaction of LA and esters. We believe that Hf-containing catalysts could be a potential candidate for the production of GVL from LA and its esters through the CTH reaction. However, it should be pointed out that most of the Hf existed in the bulk of the Hf-ATMP, which caused the low utilization of Hf atom because the Hf in the bulk was difficult to interact with the reactant, and thus a relative high molar ratio of Hf and product (0.5) is needed to obtain satisfactory catalytic activity. Designing more porous catalysts to improve the utilization of Hf may be an efficient way to enhance the activity of CTH reaction of LA and its esters with a low molar ratio of Hf and product.

ASSOCIATED CONTENT Supporting Information



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The Supporting Information is available free of charge on the ACS Publications website at DOI: XX. Calibration curves, the most plausible connectivity pattern of Hf-ATMP, physical properties of different catalysts, TEM and SEM images, and CO2-TPD for Hf-EDPA.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected], [email protected]

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS The authors thank the National Natural Science Foundation of China (21673249, 21533011, 21133009), Chinese Academy of Sciences (QYZDY-SSW-SLH013).

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Page 18 of 18

For Table of Contents Use Only

Porous Hafnium Phosphonate: Novel Heterogeneous Catalyst for Conversion of Levulinic Acid and Esters into γ-Valerolactone Chao Xie, Jinliang Song, Baowen Zhou, Jiayin Hu, Zhanrong Zhang, Pei Zhang, Zhiwei Jiang, and Buxing Han

Synopsis: Porous hafnium phosphonate was prepared and used as heterogeneous catalyst for conversion biomass-derived levulinic acid and esters into γ-valerolactone.


Porous Hafnium Phosphonate: Novel Heterogeneous Catalyst for

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