Elsevier

Catalysis Today

Volume 309, 1 July 2018, Pages 253-262
Catalysis Today

Porous iron-phosphonate nanomaterial as an efficient catalyst for the CO2 fixation at atmospheric pressure and esterification of biomass-derived levulinic acid

https://doi.org/10.1016/j.cattod.2017.05.093Get rights and content

Highlights

  • Synthesis of iron-phosphonate HPFP-1(NP) under hydrothermal conditions.

  • HPFP-1 nanomaterial showed particle size of 1.8-3.0 nm and good BET surface area.

  • HPFP-1 showed excellent catalytic activity for the synthesis of cyclic carbonates from epoxides with CO2. under atmospheric pressure and at room temperature.

  • HPFP-1 also showed good activity for the synthesis of alkyl levulinates.

  • The catalyst was stable and reusable for several cycles without losing its catalytic activity.

Abstract

Chemical fixation of CO2 and synthesis of biofuels through convenient reaction pathways are very demanding in the context of sustainable and eco-friendly catalysis. Herein, we report the synthesis of iron-phosphonate nanoparticles HPFP-1(NP) through the simple chemical reaction between hexamethylenediamine-N,N,N′,N′-tetrakis-(methylphosphonic acid) and FeCl3 under hydrothermal conditions. The material has been characterized by transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), N2 adsorption/desorption studies and FE-SEM. This porous material showed high catalytic activity for the synthesis of organic carbonates from a wide range of epoxides at room temperature in the presence of CO2 at atmospheric pressure. This nanocatalyst also exhibited excellent catalytic activity for the conversion of levulinic acid into alkyl levulinates. The HPFP-1(NP) catalyst showed high recycling efficiency in these catalytic reactions.

Introduction

CO2 is a very significant C1 feedstock in organic synthesis as it is non-flammable, non-toxic, inexpensive and abundant in nature [1]. Designing a novel and efficient catalytic system for carbon dioxide fixation is very challenging for fruitful utilization of abundant CO2 in nature and to mitigate the global warming caused by the unrestricted use of fossil fuels, industrialization and other human activities. Today large attention has been made to promote the environmentally hazardless schemes based on CO2 fixation reactions [2], [3], [4], [5], [6]. One of the useful chemical transformations of CO2 is its cycloaddition to epoxides for the synthesis of organic cyclic carbonates, which is highly demanding in polymers. These are essential starting materials for the synthesis of organic fine chemicals and pharmaceuticals in biomedical research. These cyclic five-membered organic carbonates are used as precursors of several polymeric compounds, aprotic polar solvents and electrolytes for the rechargeable batteries [7]. In the recent years, a wide range of homogenous and heterogeneous catalytic systems such as crown ether [8], ionic liquids [9] or titanosilicates [10], alkali metal salts [11], functionalized polymers [12], organic bases [13], [14], [15], organocatalysts [16], [17], mixed oxides [18], [19], metal complexes [20], zeolites [21], [22], zeolitic imidazolate frameworks [23], [24] and functionalized mesoporous materials [25], [26], [27], [28], [29] are explored in this chemical transformation. Recently, several urea derivative-based ionic liquids (UDILs) [30], metal-free tri-s-triazine terminal-linked ionic liquids [31] and binary Zn-SBA-15/KI catalysts [32] with high thermal stability have been synthesized, analyzed structurally and explored in CO2 capture and conversion under mild reaction conditions.

On the other hand, diminishing fossil fuel reserve with the rapid industrialization has a severe effect on our environment and energy resource [33]. This has motivated the researchers to focus for developing technologies for the production of fuels and platform chemicals from renewable feedstocks [34], [35], [36], [37], [38], which should have essential features like biodegradability, environmental friendliness, renewability, low-toxicity, good blending and adaptability with the present petroleum-based fuels used in engines [39]. The production of esters from levulinic acid (LA) has huge interests as LA is one of the most important platform molecules which are derived from biomass consisting of C6 sugars obtained from lingo-cellulose [40]. Among the present sources of biodiesel, ethyl levulinate (EL) is a major component obtained through the esterification of biomass derived LA with EtOH. EL has received a huge attention because it can be utilized up to 5 wt% as an additive to diesel and can be blended with most of the petroleum-based fuels [41], [42], [43], [44].

In this context it is pertinent to mention that phosphate-based porous nanomaterials are largely explored in lithium-ion batteries [45], ion-exchange [46], proton conducting material [47] etc. Whereas, there are only few reports on the catalytic potential of these materials [48]. For designing a suitable phosphate based material as heterogeneous catalyst controlled synthesis of tiny metal phosphonate particles with uniform morphology, considerably good dispersion of active metal centres and large micropores together with high BET surface area are required. Due to the presence of abundant surface phosphonate groups in the metal-phosphonate synthesized from a multidentate phosphonate precursor it may offer good catalytic activity for a wide range of solid acid catalyzed reactions. Thus, here we have synthesized Fe-phosphonate nanomaterials HPFP-1(NP) through the chemical reaction of hexamethylenediamine-N,N,N′,N′-tetrakis-(methylphosphonic acid) and aqueous solution of FeCl3 under hydrothermal conditions and explored its catalytic potential in the CO2 fixation to epoxide and esterification of levulinic acid. The HPFP-1(NP) nanoparticles showed very good catalytic activity for the production of organic cyclic carbonates from a wide range of epoxides in the presence of CO2 under atmospheric pressure maintaining eco-friendly reaction conditions. This nanocatalyst also exhibited excellent catalytic activity for the conversion of levulinic acid into alkyl levulinates under mild reaction conditions.

Section snippets

Materials

FeCl3 was procured from E-Merck. Hexamethylenediamine-N,N,N′,N′-tetrakis-(methylphosphonic acid) HDTMP and levulinic acid was purchased from Sigma-Aldrich. All epoxides and amines were also bought from Sigma-Aldrich. All solvents and reagents were distilled through standard process and dried up.

Characterization techniques

Transmission electron microscopy (TEM) images of the nanomaterials were obtained with the help of a JEOL JEM 2010 transmission electron microscope operating at 200 kV. Powder X-ray diffraction (PXRD)

Powder X-ray diffraction (PXRD) and nanostructure analysis

The powder X-ray diffraction pattern of as-synthesized organic-inorganic hybrid iron phosphonate material HPFP-1(NP) using 4:1 molar ratio of Fe(III) to HDTMP in the synthesis gel is shown in Fig. 1. As noticed from the Figure there is only two noticeable diffraction peaks, appeared at 2θ value of 5.6° and 7.8° corresponding to the two planes (001) and (100), respectively of tetragonal phase of HPFP-1(NP). This result agrees well with the hybrid iron phosphonate material HPFP-1 nanoparticles

Conclusion

In conclusion, we have synthesized organic-inorganic hybrid iron phosphonate HPFP-1 nanoparticles by using hexamethylenediamine-N,N,N′,N′-tetrakis-(methylphosphonic acid) as phosphonate precursor and it showed excellent catalytic activity for the synthesis of organic cyclic carbonates from epoxides in presence of carbon dioxide at room temperature under atmospheric pressure and efficient conversion of levulinic acid into alkyl levulinates. The HPFP-1(NP) was recycled and reused for five

Acknowledgements

SMI acknowledges Department of Science and Technology (DST-SERB, project reference no. EMR/2016/004956) New Delhi, Govt. of India and Council of Scientific and Industrial Research (CSIR, project reference no. 02(0284)/16/EMR-II) New Delhi, Govt. of India for financial support. NS acknowledges the Science and Engineering Research Board (SERB), DST, Govt. Of India, for his National Post-Doctoral Fellowship (File No.: PDF/2015/000460). PB thanks to CSIR, New Delhi, India for her senior research

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