Synergistic catalytic hydrogenation of furfural to 1,2-pentanediol and 1,5-pentanediol with LDO derived from CuMgAl hydrotalcite

doi:10.1016/j.mcat.2020.111298

Molecular Catalysis

Volume 499, January 2021, 111298

https://doi.org/10.1016/j.mcat.2020.111298 Get rights and content

Highlights

•
CuMgAl Layer Double Oxides are prepared under certain amount of copper contents.
•
The catalyst is applied in the selective hydrogenolysis of furfural to pentanediols.
•
The catalysis is determined by the synergism between copper and acid-base sites.
•
The catalytic properties of the catalyst can be maintained after five runs.

Abstract

A series of layer double metal oxides (LDO) from CuMgAl hydrotalcite precursors were prepared by urea decomposition under different calcination temperatures in this work. Various characterizations including XRD, SEM, FTIR, XPS, H₂-TPR, NH₃-TPD and CO₂-TPD were carried out to investigate the structural properties of the as-prepared samples. After calcination at certain temperatures, the resulted LDO presents the excellent catalytic property in the selective hydrogenolysis of furfural (FA) to 1,2-pentanediol (1,2-PeD) and 1,5-pentanediol (1,5-PeD). The Cu⁺/Cu²⁺ ratio and the acid-base amount from the calcination process play the key role in the catalytic performance towards this reaction. The optimal catalyst (CuMgAlO-S3) with the maximal Cu⁺/Cu²⁺ ratio and the acid-base amount exhibits the best catalytic performance towards hydrogenation of furfural to 1,2-pentanediol (selectivity 55.2 %.) and 1,5-pentanediol (selectivity 28.5 %) with more than 80 % of conversion rate, which indicated the selectivity of 1,2- and 1,5-PeDs counted on the synergistic effect of Cu⁺ and acid-base properties.

Graphical abstract

Introduction

Biomass-based furfural (FA), as an important building block for future bioreﬁnery field, has become caused extensive concern in both industry and academic researches [1]. Selective catalytic hydrogenation and hydrogenolysis of the C single bond O bond are considered to be one of the most effective methods for the conversion of FA and its derivatives to valuable chemicals such as pentanediols (1,2-PeD and 1,5-PeD) [2]. Up to now, it has been confirmed that noble metal catalysts, including supported Ru [3], Rh [4], Pt [5,6], Pd [7], etc [8]. can be efficiently applied in the furfural hydrogenolysis to form 1,2-PeD and 1,5-PeD. However, the drawbacks of high cost and scarcity would suppress the large-scale application of noble metal catalysts in this field [9]. Previous investigations have reported the successes of the noble-metal-free Cu-Cr catalyst for the hydrogenolysis of furfural [10], the potential toxicity of chromite additive is nonnegligible in this system. Therefore, to find out noble-metal-free and environmentally friendly catalysts has become the urgent need in the synthesis of pentanediols.

It was worth noting that copper-based composites [11], especially the samples with well distribution of Cu⁰ species [12], are useful catalysts in the hydrogenolysis of reactants with carbon-oxygen (C double bond O/C single bond O) bond [13], which presents high selectivity towards hydrogenation of CO bonds but inactive to the CC bonds [14]. In addition, the hydrogenation of furfural to pentanediols is a tandem reaction, which consists of the initial transfer from furfural to furfuryl alcohol [15] and followed ring-opening to acquire the target 1,2-PeD and 1,5-PeD. The first step has been verified to be responsible from the Cu⁰ serving as the active centers [16], while the acidity and alkalinity from the support can determine the ring-opening reaction. Considering for these two aspects, to assemble the well distributed Cu species [17] on the acidic support could be beneficial to this tandem reaction as required. For example, Liu et al. [12] presented the hydrogenation of furfural into pentanediols with Cu-Al₂O₃ as catalyst. The acidic Al₂O₃ support evidently has a great influence on the selectivity of pentanediols. However, the excessive acid sites introduced may promote the furfural to be reluctant to polymerization [6] and hydrolysis into levulinic acid [18], which would decline the selectivity of the target products.

Among various catalysts, the Cu based layered double oxide (LDO) exhibits its high activity in different acid promoted reactions [[19], [20], [21], [22], [23]]. This material derived from the laminal layered double hydroxides (LDHs, [M²⁺_1-x M³⁺_x(OH)₂] [Aⁿ⁻]_x/n·mH₂O) with calcination at 400−600°C [[24], [25], [26], [27]]. During this laminate collapse and structure topotactic transformation process, more active metal sites can be exposed [28]. Besides, despite hydrotalcite as well as its calcinated derivatives are typical alkaline materials, with the intriguing selection of the acidic M³⁺ species, such as Al³⁺, the acidity and alkalinity can be modulated to the approached level to avoid byproducts [29]. Therefore, the association of various transition metal elements in the LDH precursor creates a unique property to assemble different ratio of Cu active sites and the adjustable acidic sites together [30,31]. It can be beneficial in the selective synergistic catalytic reactions with the effect of multifunctional sites [[32], [33], [34], [35], [36], [37]].

In this regard, herein, we tried to develop the LDO derived from CuMgAl precursor as a better catalyst in the selective furfural hydrogenolysis to form 1,2-PeD and 1,5-PeD. The effects of the copper valence and acid-base property on the catalysts were also explored to shed light on the possible reaction mechanism for the selective hydrogenolysis of furfural.

Section snippets

Preparation of CuMgAl hydrotalcite and CuMgAl mixed oxide samples

All the chemicals used herein were with purity above 99 % and without further purification. The CuMgAl-LDH precursors were synthesized by the coprecipitation method companying with urea [38]. In a typical procedure, Mg(NO₃)₂·6H₂O, Al(NO₃)₃·9H₂O with a molar ratio of Mg/Al = 3:1, Cu(NO₃)₂·3H₂O with n(Cu)/n(Cu + Mg + Al) = 5 % were dissolved in deionized water (50 mL) to acquire solution A. CO(NH₂)₂ were dissolved in water (50 mL) to acquire solution B (n[CO(NH₂)₂]/n[NO₃⁻] = 2). Solution A and B

Characterization of catalysts

It could be observed from the XRD spectra (Fig. 1a) that the resulted CuMgAl-LDH in this work presents several characteristic diffraction peaks at 11.7° (003), 23.5° (006) and 36.7° (012), which matches well with the typical CuMgAl-CO₃-LDH phase [12]. After calcination, all these peaks of CuMgAl-CO₃-LDH have been consumed by the thermal treatment, while three broad diffraction peaks at 35.8°,43.7° and 63.8° have appeared, attributed to a mixed phase of MgO and CuO with low-crystallinity.

Conclusions

In summary, the mixed oxides derived from CuMgAl hydrotalcite with different calcination temperature were prepared. It showed remarkable catalytic performance potential towards the hydrogenation of furfural to 1,2-Pentanediol and 1,5-Pentanediol. The optimal reaction conditions were set at 150°C and 6 MPa H₂ with CuMgAlO-S3 as catalyst. After reaction, it presented 84.1 % conversion and the selectivity of 1,2-PeD and 1,5-PeD can reach to 55.2 % and 28.5 %, respectively. During the process, the

CRediT authorship contribution statement

Xiaomin Fu: Investigation, Visualization, Conceptualization, Validation, Writing - original draft, Formal analysis, Writing - review & editing. Xiaoqian Ren: Resources, Supervision, Funding acquisition, Methodology, Conceptualization, Validation, Formal analysis, Writing - review & editing. Jiecan Shen: Investigation, Conceptualization, Validation, Writing - review & editing. Yong Jiang: Investigation, Validation, Writing - review & editing. Yuehua Wang: Investigation, Validation, Writing -

Declaration of Competing Interest

The authors report no declarations of interest.

Acknowledgements

This work was supported by the National Basic Research Program of China, funded Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

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¹: These two authors contributed equally in composing it.

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Synergistic catalytic hydrogenation of furfural to 1,2-pentanediol and 1,5-pentanediol with LDO derived from CuMgAl hydrotalcite

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Preparation of CuMgAl hydrotalcite and CuMgAl mixed oxide samples

Characterization of catalysts

Conclusions

CRediT authorship contribution statement

Declaration of Competing Interest

Acknowledgements

Chem. Rev.

Catal. Rev.

Green Chem.

ACS Omega

J. Catal.

ACS Catal.

Catal. Today

ACS Sustain. Chem. Eng.

J. Hazard. Mater.

Int. J. Chem. React. Eng.

Mol. Catal.

Catal. Sci. Technol.

Mol. Catal.

Appl. Catal. B: Environ.

Mol. Catal.

Chin. J. Catal. (Chinese Version)

Chem. Soc. Rev.

ACS Catal.

Chem. Mater.

Chem. Rev.

Chem. Soc. Rev.

J. Alloys. Compd.

Catalysts

J. Environ. Manage.

J. Hazard. Mater.

J. Hazard. Mater.

ChemistrySelect

J. Mater. Chem.

Appl. Catal. A-Gen.

Appl. Clay Sci.

Appl. Clay Sci.

J. Mater. Chem. A

ACS Appl. Mater. Interfaces

React. Kinet. Mech. Catal.

React. Kinet. Mech. Catal.