A Cu-based MOF for the effective carboxylation of terminal alkynes with CO2 under mild conditions

doi:10.1016/j.jcou.2020.101177

Journal of CO2 Utilization

Volume 39, July 2020, 101177

https://doi.org/10.1016/j.jcou.2020.101177 Get rights and content

Highlights

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A Cu-based MOF is applied as effective catalyst for CO2 carboxylation of terminal alkynes.
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The Cu(IN)-MOF exhibited excellent catalytic performance.
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The Cu(II) was reduced to Cu(I) by alkynes during reaction enhancing the catalytic performance.
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Cu(IN)-MOF is a heterogeneous catalyst exhibiting an excellent recyclability.

Abstract

The coordination of pyridylcarboxylate (isonicotinic acid, IN) with copper (II) fabricates a Cu(IN)-MOF. The characteristic properties of the Cu(IN)-MOF are obtained via different analysis techniques such as XRD, SEM, BET, ICP, TG, etc. The advantage of copper(II) coordinated with a bi-functional organic linker (IN), containing a pyridyl and carboxylate group, is demonstrated by the chemical properties of which the Cu(II)-based MOF exhibits excellent catalytic performance for the CO₂ carboxylation of terminal alkynes. No noble-metal, co-catalyst, or additives are required to execute the reaction. The effectiveness of the Cu(IN)-MOF was demonstrated with a variety of substrates (>11). Moreover, the Cu(IN)-MOF, as a heterogeneous catalyst, can be recycled at least 5 times retaining its excellent catalytic performance. Herein, we report the first copper (II) metal-organic framework (Cu(IN)-MOF) applied for the carboxylation of alkynes with CO₂ demonstrating several advantages such as stable catalyst, avoiding the use of an expensive noble-metal, straightforward synthesis.

Graphical abstract

Introduction

Nowadays, environmental problems are more and more of concern and are mainly introduced due to the incredible expansion of the human population and the acceleration of economic activity to enhance the development of countries. Consequently, one of the main by-products generated from social activities is carbon dioxide (CO₂), which exposes a negative impact on the environment. Currently, the concentration of CO₂ in the atmosphere demonstrates a sustainable increase year by year. Capturing and utilizing CO₂ as a C1 feedstock to synthesize fine chemicals is of much interest because of energy, and environmental issues [1,2]. Additionally, the direct usage of CO₂ as a carbon source, a highly functional, abundant, inexpensive, non-toxic, and renewable C1 resource, is an emerging strategy [[3], [4], [5]].

Meanwhile, the exploration of new pathways in chemical reactions is a great challenge to develop new technologies for chemical syntheses. An effective process in chemical technology with an environmentally friendly method would include a heterogeneous catalyst, mild reaction conditions (low-temperature pressure), etc., could be another approach to solve the CO₂ emission. In this regard, the efficient transformation of CO₂ with epoxides, propargylic alcohols, amines, alkenes, or alkynes via a carboxylation reaction has evoked considerable interest from both industrial and academic viewpoints [[6], [7], [8]]. The resulting carboxylated products are a series of versatile compounds with broad applications in organic synthesis and of which some have potential bioactivity suitable for pharmaceutical usage. Notably, the direct carboxylation of CO₂ into terminal alkynes is highly attractive. In this way, a substantial amount of CO₂ can be converted into carboxylic acids that are widely used in agrochemicals, bioactive molecules, pharmaceuticals, and conductive polymers [[9], [10], [11], [12]]. Generally, the principal mechanism is the insertion of CO₂ into a carbon-metal bond with the formation of unsaturated nucleophilic species [13]. However, harsh or critical reaction conditions are required for CO₂ insertion into organic compounds due to the high thermodynamic and kinetic stability of CO₂.

Over the past decades, various catalysts have been developed that exhibited a compelling performance to transform CO₂ with terminal alkynes into propiolic acids. Noble metals such as silver (Ag), ruthenium (Ru), palladium (Pd), or their metal complexes are usually required as active sites in the catalytic system [[14], [15], [16], [17], [18], [19]]. Unfortunately, the high metal loading, high cost of the noble-metal, low air and moisture stability of their complexes, and complex catalysis synthesis, etc., are a barrier in catalyst development for practical and large scale industrial applications. Concerning green and sustainable chemistry, there are many additional advantages to apply heterogeneous catalysts. Advantages such as more straightforward workup and purification, less waste disposal, reduction or elimination of corrosion problems, continuous process operations, and recycle ability, etc. are most attractive. Recently, metal-organic frameworks (MOFs) have attracted a lot of interest in possible applications in catalysis [[20], [21], [22]]. MOF structures contain a variety of metal species and different functionalized organic linkers. Moreover, the pore tunability makes them excellent candidates for heterogeneous catalysts. Furthermore, structure modification or functionalization (as-synthesis or post-synthesis) allows tuning of active sites enhancing the catalytic performance [23,24]. Thus the outstanding MOF properties make them attractive materials for catalytic applications. However, only some reports about MOFs catalyzing the CO₂ carboxylation with terminal alkynes demonstrating promising results are available. Relevant achievements based on post-modification synthesis via Ag nanoparticles encapsulation in MOFs (Ag@MIL-101) were described [25]. Recently, the synergetic bimetallic CuI and Gd-clusters bridging with isonicotinic acid [Gd₃Cu₁₂I₁₂(IN)₉(DMF)₄]_n·nDMF and [Gd₄Cu₄I₃(CO₃)₂(IN)₉(HIN)_0.5(DMF) (H₂O)]_n·nDMF·nH₂O were reported for the carboxylation reaction in the presence of n-BuI [26]. The active centers were situated on the Gd-clusters and Cu-clusters (Cu₁₂I₁₂ or Cu₃I₂). Nonetheless, the systems appeared to be unstable since no recycling was reported. Despite this progress, there are only a limited number of catalysts developed for this carboxylation reaction. Therefore, the design of a novel catalyst (heterogeneous) based on earth-abundant metals having a high efficiency under mild conditions is still highly challenging.

Inspired by copper metal-based catalysts, which are cost-effective, we herein report, a copper (II) based MOF (Cu(IN)-MOF) applied as a heterogeneous catalyst for the CO₂ carboxylation with terminal alkynes. Thermal stability and porosity, beneficial for CO₂ adsorption, are properties that could promote the catalytic performance. This work is the first reported copper (II) based MOF (Cu(IN)-MOF) applied as a catalyst for the CO₂ carboxylation with terminal alkynes. The catalyst is free of noble metals, chemical and thermally stable, inexpensive and demonstrates an efficient performance under mild reaction conditions (ambient CO₂ pressure) for the CO₂ carboxylation.

Section snippets

Materials

All the reagents, copper acetate monohydrate (Cu(CH₃COO)₂·H₂O), isonicotinic acid (IN), N,N-dimethylformamide (DMF), cesium carbonate, methanol, phenylacetylene, dichloromethane (DCM), hydrochloric acid, diethyl ether, and 1,3,5-trioxane were purchased from Aladdin chemical. The deuterated chloroform was provided from Sigma-Aldrich. All chemicals and solvents were used without any further purification.

Catalyst synthesis

The Cu(IN)-MOF was synthesized applying the solvothermal method following a previous report,

Catalyst characterization

Coordination polymers or metal-organic frameworks based on copper (II) bridging with a pyridylcarboxylate ligand (isonicotinic acid, IN) were synthesized and denoted as Cu(IN)-MOF. The dinuclear copper (II) nodes binding with both of pyridyl (N-) and carboxylate (COO-) groups balancing the metal charge were investigated. The single-crystal structure of Cu(IN)-MOF was firstly reported by Lu and Babb [28]. However, differences in the crystal structures might occur depending on the synthesis

Conclusion

A copper (II) based MOF was achieved using a bifunctional ligand (isonicotinic acid) generating a unique Cu(IN)-MOF. The characterization revealed a crystalline structure with 2D plate-like morphologies having a small surface area but high thermal stability up to 300 °C. Further, the Cu(IN)-MOF was applied for the direct CO₂ carboxylation and demonstrated an excellent catalytic performance using a variety of terminal alkynes, revealing a high tolerance towards functional substituents.

Author contributions

S.C. and F.V. devised the concept for the work and designed the experiments. G.S., W.X. and J.W. synthesized the materials and carried out the characterizations. G.S. and W.X. performed the catalysis. GS., S.C., and F.V. wrote the manuscript. All the authors revised the manuscript. F.V. supervised the whole work.

Declaration of interests

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

The authors are grateful to the State Key Lab of Advanced Technology for Materials Synthesis and Processing for financial support (Wuhan University of Technology). S.C. acknowledges the support of the National Natural Science Foundation of China (Nos. 21850410449, 21950410754). F.V. appreciates the financial support from the Tomsk Polytechnic University Competitiveness Enhancement Program grant (VIU-69/2019).

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A Cu-based MOF for the effective carboxylation of terminal alkynes with CO2 under mild conditions

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Catalyst synthesis

Catalyst characterization

Conclusion

Author contributions

Declaration of interests

Acknowledgments

Coord. Chem. Rev.

Curr. Opin. Green Sustain.

Asian J. Org. Chem.

Inorg. Chem. Commun.

Microporous Mesoporous Mater.

Microporous Mesoporous Mater.

Carbon dioxide utilisation for production of transport fuels: process and economic analysis

Energy Environ. Sci.

Life cycle assessment of polyols for polyurethane production using CO2 as feedstock: insights from an industrial case study

Green Chem.

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Chem. Rev.

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ChemSusChem

CO2 = CO + [O]: recent advances in carbonylation of C–H bonds with CO2

Chem. Commun.

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ChemCatChem

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Synthesis of carboxylic acids and esters from CO₂

C− H carboxylation of aromatic compounds through CO₂ fixation

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