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Progress on Catalyst Development for Direct Synthesis of Dimethyl Carbonate from CO2 and Methanol

  • Somboon Chaemchuen
  • Oleg V. Semyonov
  • Jannes Dingemans
  • Wei Xu
  • Serge Zhuiykov
  • Anish Khan
  • Francis VerpoortEmail author
Review

Abstract

The reaction of carbon dioxide transformation is tremendously interesting in research societies from the viewpoint of carbon resource and also to resolve the environmental problem of carbon dioxide emission. Carbon dioxide (CO2) is a suitable C1 feedstock which can be converted into a number of valuable fine chemicals. The utilization of CO2 not only helps to reduce the carbon emission but should also lead to economic benefits, if CO2 is converted into chemicals for which there are significant demands or have a high added value. The reaction of CO2 with methanol is one of the pathways to directly synthesize dimethyl carbonate. However, the catalyst is a key factor in the reaction development. Herein, in this review, the focus is made on materials for the catalyzed reaction for the direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol. The developed catalysts (homogeneous and heterogeneous catalysts) used so far are discussed, together with the respective operating conditions to obtain the optimum catalyst performance. Interesting ideas to allow the direct synthesis of carbonate products from CO2 with methanol using developed novel catalysts with high performance and efficiency for the economy are offered in this review.

Keywords

Dimethyl carbonate Linear carbonate Catalyst CO2 utilization Methanol 

Abbreviations

DMC

Dimethyl carbonate

DME

Dimethyl ether

MeOH

Methanol

IL

Ionic liquid

[C2-mim][MeO]

1-Ethyl-3-methylimidazolium methoxide

[C4-mim][MeO]

1-Butyl-3-methylimidazolium methoxide

[BA][MeO]

Benzylalkonium methoxide

EtmimOH

1-Ethoxyl-3-methylimidazolium hydroxide

EtmimBr

1-Ethoxyl-3-methylimidazolium bromide

EmimOH

1-Ethyl-3-methylimidazolium hydroxide

BmimOH

1-Butyl-3-methylimidazolium hydroxide

CH

Choline hydroxide (Basic IL)

BzMDH

Benzylmethyldihydroxyethyl ammonium hydroxide

MTH

Methyltrihydroxyethylammonium hydroxide

BzTH

Benzyltrihydroxyethylammonium hydroxide

THH

Tetrahydroxyethylammonium hydroxide

BMDH

Butylmethyldihydroxyethyl ammonium hydroxide

[bmim][Cl]

1-Butyl-3-methylimidazolium chloride

[bmim][BF4]

1-Butyl-3-methylimidazolium tetrafluoroborate

[bmim][PF6]

1-Butyl-3-methylimidazolium hexafluorophosphate

[bmim][Tf2N]

1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

[emim][BF4]

1-Ethyl-3-methylimidazolium tetrafluoroborate

[emim][Tf2N]

1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

[mbmim][Tf2N]

1-(3-Methyl)butyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide

[dmbmim][Tf2N]

1-(3,3-Dimethyl)butyl-3methyl imidazolium bis(trifluoromethylsulfonyl)imide

[bpy][Cl]

N-Butyl-pyridine chloride

[bpy][BF4]

N-Butyl-pyridine tetrafluoroborato

[bpy][PF6]

N-Butyl-pyridine hexafluorophosphate

[bpy][Tf2N]

N-Butyl-pyridinebis (trifluoromethylsulfonyl)imide

[epy][BF4]

N-Ethyl-pyridinetetrafluoroborato

[epy][Tf2N]

N-Ethyl-pyridine bis(trifluoromethylsulfonyl)imide

[dmbpy][Tf2N] DBU

1-(3,3-Dimethyl)butyl-pyridine bis(trifluoromethylsulfonyl)imide 1,8-diazabicycloundec-7-ene

2-CP

2-Cyanopyridine

MTCL

Methyl trichloroacetate

1 Introduction

Currently, plenty of carbon dioxide (CO2) deriving as a by-product from energy production from oil, coal, and gas, etc., is continuously released into the atmosphere. The high concentration of CO2 in the atmosphere causes global climate change, as it is a greenhouse gas. The development of processes utilizing CO2 is an alternative route to reduce CO2 emission in the atmosphere as well as the research towards alternative energy source which is more environmentally friendly. Meanwhile, strategies to capture carbon dioxide or storage (CCS) are currently used to reduce CO2 emission from fossil fuel power station. Taking advantages of CO2 of being an abundant resource, economically attractive, non-toxic, and a renewable carbon C1 source, converting CO2 to fine chemical products is highly desirable [1, 2]. Furthermore, the production of commercially important chemicals via simultaneously CO2 capture (CCS) and utilization could be the best strategy for the chemical industry as well as for the reduction of CO2. Currently, the biggest utilized CO2 feedstock amounts to 90 Mt yearly in the urea production which have been a commercial process since 1922 [3]. Still, there are several potential reaction to convert CO2 into useful chemicals such as CO2 reduction under photochemical or electrochemical conditions producing CO/formic acid/CH4/methanol, biological CO2 conversion into ethanol/sugar, CO2 reforming into synthesis gas (CO/H2), or CO2 fixation with organic compounds producing carbonate, etc.

Examples of CO2 conversion to organic compounds are summarized in Scheme 1. In this review, the aim is to provide an overview of the different processes to obtain linear carbonates using CO2 as a raw carbon source.
Scheme 1

The optional in CO2 conversion reaction producing a fine chemical

Incorporation of CO2 into organic derivatives producing carbonate compounds is one potential route for CO2 transformation and of significance for the reduction of carbon emission. Currently, several investigations have reported the synthesis of organic carbonates via CO2 addition reaction. The organic carbonates are wildly used for several applications such as green solvents [4, 5, 6], additives to gasoline [7, 8], thickeners for cosmetics, electrolytes for batteries [9, 10, 11, 12], etc. Thus, this CO2 fixation reaction has potential for the environment by using CO2 as a C1 source from and also provides economic benefits.

Dimethyl carbonate (DMC) is an organic carbonate which is used as an electrolyte for lithium batteries and as a protic polar solvent [9]. Moreover, the high octane number and low Reid vapor pressure (RVP), reducing the CO and NOx emission after combustion, attracted considerable attention to use DMC as a fuel additive [13]. The potential demand for DMC as a fuel additive is greater than 30 Mt per year, however, the annual production is still much smaller [7, 8]. DMC could replace the toxic conventional methylating and carbonylating reagents such as methyl iodide, dimethyl sulfate, carbon monoxide, etc. [14].

Furthermore, it is also applied as a substitute for phosgene, an intermediate for the production of polycarbonates or polyurethanes [15, 16]. An overview of DMC utilization is summarized in Table 1 [16, 17].
Table 1

The dimethyl carbonate (DMC) applications

Application

Description

Reactant

Using DMC as a mediated compound in the methylation and carboxymethylation reaction to convert it into added-value chemicals instate of using toxic and corrosive phosgene and dimethyl sulfate or methyl halide, Using DMC to produce aromatic polycarbonates through diphenyl carbonate

Solvent

Using DMC as an alternative for ketones and acetate esters for paint industries, DMC has a high performance as a non-aqueous electrolyte for lithium batteries. The low toxicity and low emissions properties of DMC could be used as a generic solvent

Fuel additive

Due to the high oxygen content of DMC (53%) and high octane number, DMC enhances the performance when mixed in gasoline. Moreover, not only promote the performance of diesel but also reduces the sulfur, aromatic and soot emissions

2 Dimethyl Carbonate Synthesis

Processes for CO2 utilization consume large amounts of energy to perform the reaction due to the high stability of CO2 although some reactions have negative reaction enthalpies. For example, ∆Hr = − 40.7 kJ mol−1 for the synthesis of benzoic acid from benzene and CO2, or ∆Hr = − 16.6 kJ mol−1 for the synthesis of acetic acid from CO2 and methane [18]. However, the synthesis of organic carbonates, which can be classified into cyclic and linear carbonates, as a target of CO2 utilization seems to be more suitable from a thermodynamic point of view based on the modeling and kinetic experiments [19]. This is also true for the organic carbonates currently used in industry such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), and diphenyl carbonate (DPC). These organic carbonates are useful intermediates for manufacturing polycarbonates or electrolytes for lithium batteries.

The traditional route to synthesize DMC in industry proceeds via the reaction of carbon dioxide with methanol in the presence of phosgene (Scheme 2) [1, 13]. Later, a process using carbon monoxide with methanol in the presence of oxygen (oxidative carbonylation) was developed [20]. Finally, the reaction of CO2 with ethylene oxide producing ethylene carbonate followed by an ester exchange with methanol was reported. Recently, the electrochemical oxycarbonylation of methanol has been proposed [21]. However, all these processes use toxic, corrosive, flammable and explosive gases such as phosgene, hydrogen chloride, and carbon monoxide and are energy consuming processes. Direct formation of dimethyl carbonate (DMC) from CO2 and methanol is potentially the most straightforward process for the synthesis of organic carbonates (Schemes 3). The DMC synthesis directly from CO2 has several advantages (1) a single process or a one-step process with less waste resulting in a high atom economy, (2) alternative for processes with toxic and expensive materials, (3) high abundance of the raw materials, and (4) a green reaction combined with carbon recycling.
Scheme 2

Dialkyl carbonate synthesis with phosgene

Scheme 3

Dialkyl carbonate synthesis with CO2

However, critical reaction conditions of high temperature and pressure are required which is a drawback for the direct DCM synthesis from CO2 and methanol. Additionally, the high temperature decreases the product selectivity due to DMC decomposition. Furthermore, for the linear carbonates synthesis (such as DMC) from alcohol and CO2 generates water as a by-product (Scheme 3). Unfortunately, water generates hydrolysis of the catalyst causing decomposition of the catalyst during the reaction, resulting in a low catalytic performance and poor product yields. To shift the equilibrium to the product side, it is necessary to remove water from the reaction mixture and simultaneously increase the CO2 concentration (pressurizing) generating additional DMC. Addition of organic dehydrating agents to the reaction mixture could be an option to shift the equilibrium. The inorganic or adsorbent materials such as sodium sulfate, magnesium sulfate, dicyclohexyl carbodiimide, trimethyl phosphate, and molecular sieves have a negligible effect on the amount of product formed [22, 23]. The dehydration strategy, using dehydration agents, has been reported in different ways such as simple dehydration of methanol before the reaction [24], the use of organic molecules as a dehydrating agent [25, 26], incorporation of a dehydration unit filled with inorganic (zeolite) materials [27, 28], and the use of a membrane reactor for selective water removal [29]. Further development of the industrial process for water removal, improving the DMC yield, was investigated by adding a dehydration section and circulation of the reaction mixture (Fig. 1a). The molecular sieves having a pore size of 3Å were packed in the dehydrating section at room temperature. In the absence of the dehydrating part, the yield of DMC is saturated at a very early stage, showing the thermodynamic limitation. On the other hand, in the presence of the dehydrating unit, the DMC yield increases as the reaction time proceeds and eventually achieves nearly a 50% yield based on methanol charged (Fig. 1b). In addition, in the presence of the dehydrating part, the DMC yield increases in proportion to the catalyst amount and the reaction pressure. The DMC formation is very selective and byproducts such as dimethyl ether are not observed.
Fig. 1

Diagram of DMC synthesis using an inorganic dehydrating unit (a) and the time dependence of DMC yield (b).

Figure copy with permission from Ref. [1]

Recently, an effective and continuous production process of DMC from CO2 and methanol using a fixed-bed reactor filled with a ceria catalyst in the presence of 2-cyanopyridine as a dehydrating agent has been reported [30]. The system was developed employing information from the batch reaction system [31, 32]. The design process with a high-pressure system is depicted in Fig. 2. The excellent methanol conversion (> 95%) and high DMC selectivity (> 99%), gave a high weight time yield of ca. 1 gDMC g cat −1  h−1. A delicate balance between temperature, pressure, and residence time exists to achieve an excellent catalytic performance. This result revealed the highest catalytic performance for the DMC synthesis comparable with a continuous flow fixed bed reactor. Dehydrated derivatives of alcohol, such as cyclic ethers, ketals, and orthoesters have been proposed to avoid hydrating the reaction mixture. However, cyclic ethers or epoxide easily react with CO2 generating cyclic carbonates due to their ring strain. Consequently, linear ethers are less strained and thus less reactive meaning that the cyclic carbonates are easier generated then linear carbonates.
Fig. 2

Schematic process flow diagram for the continuous production of DMC. Figure copy with permission from Ref. [30]

The DMC synthesis through cyclic carbonates is an option to avoid dehydration. Furthermore, the epoxide can react also with CO2 to yield alkylene carbonates and when a large excess of methanol is used DMC can be produced. An excess of methanol is required due to the unfavorable ester exchange between methanol and alkylene carbonates. Table 2 summarizes typical catalytic systems for this reaction route. Suitable catalysts need to activate both steps (a) and (b), and generally, basic compounds seem appropriate.
Table 2

Dimethyl carbonate synthesis from epoxides, methanol, and CO2

3 Catalyst Systems for the Direct DMC Synthesis

It is well known and wildly accepted that CO2 molecules are thermodynamically highly stable and large energy is required for the chemical transformation or critical conditions need to be applied. CO2 displays a strong affinity toward nucleophilic molecules and thus rapidly reacts with basic compounds. Furthermore, CO2 reacts with reagents such as water, alkoxides or amines, etc., producing carboxyl or carboxylate groups in the product compound, see the pattern (a) Scheme 4. Further reaction of the later leads to the formation of organic carbonates and carbamates via an electrophiles mechanism [1]. The reaction with unsaturated compounds and CO2 forms five-membered metallalactones in the presence of low valent metal complexes. Because the valence of the metal increases by two, this type of reaction is an example of an “oxidative cycloaddition” (pattern (b), Scheme 4) [33].
Scheme 4

Typical transformations of CO2. Figure copy with permission from Ref. [33]

The reaction mechanism of the direct DMC synthesis based on acid-based active sites has been investigated using infrared spectroscopy [34]. The first step is dissociative adsorption of methanol to form methoxide species. Secondly, CO2 insertion results in the formation of monomethyl carbonate, an important intermediate in the DMC synthesis. Finally, a methyl group from the adsorbed methanol is transferred to the monomethyl carbonate to form DMC. The simulation study in thermodynamic DMC synthesis revealed that a lower temperature and a high pressure of CO2 were favoring the DMC product. This is in contrast with the condition for DME production where a high reaction temperature and low CO2 pressure are favored [35].

3.1 Homogeneous catalyst

Ionic liquids (ILs) are salts in the liquid state at room temperature which are wildly applied as catalysts and solvents [36]. Their characteristics are a wide liquid range, non- volatility, and adjustability

of their physicochemical properties. Several organic reactions such as Friedel–Crafts alkylation [37], olefin dimerization [38] and Diels–Alder reaction [39], etc., have applied ionic liquid as a catalyst and observed an excellent yield and selectivity. The direct use of hydroxyl-functionalized ionic liquids as a catalyst for DMC synthesis from MeOH and CO2 has been reported also. The reaction mechanism of the direct DMC synthesis from CO2 and methanol based on the ionic liquid catalyst is given in Scheme 5. The hydroxyl-functionalized basic ionic liquid catalyzes the reaction via the activation of reactant molecules (methanol and CO2). The reaction mechanism using ionic liquids illustrates that the basic ionic liquid activates methanol forming a methoxide anion (CH3O).
Scheme 5

The reaction mechanism of an ionic liquid as a catalyst [40]

Then, the methoxide anion (CH3O) performs a nucleophilic attack on the carbonyl carbon that was activated by the functionalized ionic liquid generating the intermediate CH3OCOO. The hydroxyl of IL coordinately interacted with oxygen and/or hydrogen atoms of CH3OH molecules generating a hydrogen bond network, which results in a weakening of the C–O bonds. The OH anions make a nucleophilic attack on the positively charged carbon atom of methanol. As a result, methyl cations (CH3+) are easily produced. Finally, the activated CH3+ reacts with the intermediate CH3OCOO to produces the target product DMC and releases the base OH, realizing the catalytic cycle. The Brönsted basicity of the ionic liquid plays a key role for fixating and activating CO2 and methanol [40]. Moreover, a cation with a shorter carbon chain length exhibited relatively higher activity due to a higher polarity. The basic anion OH of the hydroxyl alcohol displayed a synergic effect for the fixation and activation of CO2 and methanol. The effect of hydroxyl-functionalized ionic liquids such as dialkyl (or alkyl) di- (tri-) hydroxyethyl ammonium hydroxide, tetrahydroxyethyl ammonium hydroxide, and alkylhydroxyethyl or dihydroxyethyl imidazolium hydroxide were investigated [41]. The conjugation of benzyl substituents on the cation, e.g. benzylmethyldihydroxyethylammonium hydroxide (BzMDH) vs. butylmethyldihydroxyethylammonium hydroxide (BMDH), had a positive effect on the carboxylation of methanol. Later on, the immobilized BzMDH supported on SBA-15, CNT, CaO, and LDHs were developed and further studied as a heterogeneous catalyst. The BzMDH/CaO was found to possess a higher activity as compared with other supported catalysts originating from the water adsorption ability of CaO and thus promoting the reaction equilibrium shifting to the DMC side.

Ionic liquids containing a methoxide species as anion and imidazolium or benzylalkylammonium as cation were applied too in the direct DMC synthesis [42]. The activated species subsequently reacted with CO2, activated by the ionic liquid, resulting in the formation of DMC. Moreover, the addition of methoxide ionic liquid was important to circumvent the thermodynamic restriction via the removal of water and thus consequently shifting the equilibrium towards enhanced yields of DMC. Furthermore, higher reaction temperature and increased amount of ionic liquid were investigated revealing that the DMC formation reduced under these conditions. The dehydration of methanol to dimethyl ether at higher reaction temperature and higher viscosity after increasing the ionic liquid amount were the main reasons for lower DMC formation [43, 44]. In another report, microwave irradiation was applied for enhancing the CO2 activation in ionic liquids [45]. The energy provided by the microwave radiation promoted the mass transfer in the IL, and consequently, increased the probability of molecular collisions and reactivity of CO2.

So far, organometallic tin (IV) complexes were reported for the direct DMC synthesis and exhibited high selectivity [23, 46, 47, 48]. The organotin oxide species were generated as intermediate from the catalyst n-Bu2Sn(OCH3)2 during the reaction and prompted the catalytic performance to produce DMC [48]. The high initial rate was observed in the preliminary kinetic study, but reversible poisoning by water (by-product) revealed to deactivate the carbonate formation.

The organometallic compounds such as n-Bu2Sn(OMe)2 [49, 50], metal(IV) tetra-alkoxide [22], magnesium dialkoxide [51] have been wildly applied as a homogeneous catalyst. However, the catalyst deactivation due to the by-product formation (water) is the main drawback for those catalysts. In order to avoid the organometallic catalysts, metal acetate sources were applied also for the direct DMC synthesis of which nickel acetate demonstrated the highest yield and DMC selectivity compared with Mn, Co, Cu, Zn, Hg sources [52]. Using nickel acetate at moderated temperatures (305 K) and 10 MPa 3% DMC yield was obtained. The mechanism for the DMC formation catalyzed by metal acetate sources suggests first the formation of metal methoxide in the present of bases followed by the CO2 insertion in the metal methoxide carbonate. The further action between methyl acetate and carbonate species led to the production of DMC. This catalyst showed higher activity in the presence of water. However, the temperature and pressure strongly influenced the selectivity of this catalyst, leading to the production of methyl acetate as a secondary product [43].

3.2 Heterogeneous Catalyst

A significant drawback of homogeneous or liquid phase catalysis is (a) difficult recovery of the catalyst, (b) reaction conditions require high pressure, (c) rapid catalyst deactivation. The problems associated with liquid phase processes can be resolved by the development of an effective heterogeneous catalyst. From an economic and environmental viewpoint, there is currently much interest in the development of novel highly reactive heterogeneous catalysts that allow the synthesis of dimethyl carbonate under more economic conditions [53].

3.2.1 Metal Oxide Based Catalyst

The zirconium oxide (Zr) is a well-known alternative for organotin catalysts for the direct synthesis of DMC. The calcination of commercial zirconium hydroxide (ZrO2·xH2O) at 370 °C and applied as a heterogeneous catalyst based metal oxide was reported recently [54, 55]. The DMC yield reached 1% at 160 °C under 5 MPa CO2 pressure with ZrO2 as catalyst The impact of the crystal phases of ZrO2 on the reaction mechanism of DMC synthesis was examined by density functional theory (DFT) [56]. The c-ZrO2(1 1 1) showed the highest catalytic activity followed by m-ZrO2(1 1 1) and t-ZrO2(1 0 1), respectively. The activity of the later was so low since the t-ZrO2(1 0 1) surface showed the lowest value of activation free barriers on the rate controlling steps reaction. Among the metal oxide based catalyst cerium oxide (CeO2) demonstrated a promising performance for the direct DMC synthesis from MeOH and CO2. CeO2 is also a reference catalyst for the synthesis of DMC, showing higher activity than ZrO2 as demonstrated by Yoshida et al. [57]. The proportion relation between specific area and activity was optimal for CeO2 calcinated at a temperature of 600 °C. Furthermore, a synergetic effect was observed when using a mixture of CeO2/ZrO2 which enhanced the catalytic performance [58, 59]. The reaction was carried out at 110 °C and 0.6 MPa reaching a DMC yield of 0.83% after 4 h. Moreover, a large crystal size of the catalyst resulted in a smaller number of surface-active atoms which reduced the catalytic performance.

The morphologies of the catalyst were also reported to influence the catalytic performance. The CeO2 morphologies such as cube, rod, spindle, and irregular, etc., were synthesized and studied as a catalyst in a batch reaction [60]. Furthermore, the catalytic activity correlates with the concentration of acid and base sites of medium strength and defect sites present in CeO2. The influence of the morphology of CeO2 on the product distribution (in mmol) and mass balance (liquid product) was investigated. The Ce-spindle morphology generated the highest selectivity of DMC over the rod, cube, and irregular morphologies, respectively. The mass balance was 100% with Ce-spindle, while only 91% with Ce-rod and Ce-cube, and 86% with Ce-irregular catalysts. The high amount of defects in the Ce-spindle morphology can adsorb more CO2, which is further activated by the base sites of medium strength present in the catalyst. Additionally, a similar investigation observed that the nanorods exhibited higher activity than nanocubes and nano-octahedra, and illustrated that this observation was related to the defect density and amount of acid-basic sites [61].

The heterogeneous catalyst for CO2 methanation reaction is a reaction which involves reactant diffusion, adsorption, surface reaction, products desorption, diffusion and so on. The surface properties of the catalyst correspond with the catalytic performance and hence are of major importance. The catalyst surface contains oxygen vacant sites and has been reported to influence the catalytic activity by promoting the adsorption and activation of CO2. Therefore, the oxygen vacancies have been proposed to serve as active sites that promote the CO2 conversion in the CO2 methanation [62]. The strategy to design oxygen vacant sites was studies on CeO2 nanorods via doping with Zr atoms into the ceria lattice [63]. The Zr-doped material generated a fluorite-like solid solution that enhanced the CO2 adsorption on the oxygen vacancies to form bidentate coordinated carbonate as an intermediate able to participate in the reaction. The surface oxygen vacant sites served as Lewis acid sites that promoted the CO2 adsorption [64, 65, 66]. From this study, the relationship between the surface oxygen vacancies, CO2 adsorption capacity, and catalyst activity was clearly demonstrated. The surface oxygen vacancies on the catalyst surface were also investigated via Ni doping on CeO2 [62]. This Ni-based catalyst exhibits excellent catalytic hydrogenation and methanation performance [67, 68]. Recently, CeO2 nanorods doped with TiO2 were investigated. The TiO2 promoted the surface acid–base sites which enhanced the catalytic activity compared with pure CeO2 nanorods [69]. The TiO2-doped CeO2 catalysts showed enhancements in the redox reactions and were assisted by the oxygen deficiency and acidity of the surface [70, 71]. A variation in the amount of Ti-dopant (Ti0.06Ce0.94O2, Ti0.08Ce0.92O2, and Ti0.1Ce0.9O2) was made and showed that a lower surface area of the catalyst resulted in a lower observed catalytic performance. Lower catalytic activity was observed because less active sites were exposed on a smaller surface area [72, 73]. In addition, according to the mechanism for the DMC synthesis, from methanol and CO2, the increased amount of moderately acidic and basic sites with the addition of TiO2 contributes to the increased performance. Iron(III) oxide, a low cost and eco-friendly metal with acidic and basic sites, was proposed for the modification of ZrO2 [74]. The improved acidic and basic properties of the surface of Fe-ZrO2 catalyst were clarified by the relationship between the surface structure, acid–base property, and the catalytic performance. XRD analysis described the iron-zirconium solid solution formation (Fe0.3Zr0.7Oy) and a decline of the zirconia phase to a broad peak. However, the hexagonal crystal structure of Fe2O3 which is similar to the pure Fe2O3 was observed at high Fe content. While the specific surface area significantly increased upon raising the Fe content, this might cause the exposure of more active sites and thus lead to higher catalytic activity. The Fe-Zr solid catalysts exhibited higher catalytic activities than ZrO2 and Fe2O3 which was attributed to the increased amount of moderately acidic and basic sites after the addition of Fe. The relationship between catalytic activity and the amount of moderately acidic and basic sites, respectively, are presented in Fig. 3.
Fig. 3

The relationship between the catalytic performance and the amount of moderately acidic sites (a) and the amount of moderately basic sites (b). Figure copy with permission from Ref. [74]

Mixed oxide catalysts contain both basic and acid sites, moreover, these materials exhibit higher chemical stability as compared to single metal oxides. The cerium-calcium (Ce–Ca) was prepared by the surfactant templating approach. Addition of CaO to a CeO2 matrix caused changes in the catalyst structure as the cerium reflection in the XRD spectrum decreased. It was reported that the catalytic activity and specific area generally decreased with an increase in crystallinity and crystallite size [75]. The mixed Ce/Ca ratio 1:1 demonstrated a higher catalytic activity over the 3:1 or 1:3 ratio which was a result of the acid/basic site density [76]. Moreover, the surface oxygen vacancies on the surface of the catalysts were investigated since the addition of different amounts of CaO could affect the structure and surface properties [77]. The acid–base properties and amount of surface oxygen vacancies on the surface of the catalysts were improved due to the interaction between CaO and CeO2, and the oxygen vacancies enhanced the adsorption of CO2. Similar strategies were also applied to ZrO2–MgO. The tuning ratio of bimetallic catalysts widely evidenced to enhance the catalytic properties for the reaction. Nevertheless, for an efficient synthesis of carbonates from CO2, a balance between basic and acidic centers on the catalyst surface is needed [78, 79]. Therefore, the surface modifications of active metal oxides were investigated. ZrO2 was modified with phosphoric acid, a weak Brønsted acid, of which the additional Brønsted acid sites could contribute to MeOH activation and enhanced the catalytic activity [55, 80]. Recently, the phosphoric acid surface treatment of CeO2–ZrO2 has been reported [81]. The phosphate modification caused a decrease of moderate and strong basic sites and an increase of Lewis acidic sites from most likely unsaturated surface Zr4+ cations which are responsible for an enhanced ability to form monodentate methoxy species as an intermediate in the catalytic cycle. The acidic compounds of ammonium triflates such as [Ph2NH2]OTf and [C6F5NH3]OTf, were added as a co-catalyst with Bu2SnO or Ti(O-i-Pr)4 catalyst [26]. Since the acidic compounds generally promote the esterification of carboxylic acid, a small amount of co-catalyst remarkable enhanced the DMC yields; more than double of the yield compared with the reaction without co-catalysts. However, the commercial Brönsted acids such as HCl, H2SO4, and H3PO4 resulted in no remarkable increase of DMC yields while p-toluene sulfonic acid gave a slightly positive effect. The triflate salts (co-catalyst) accelerated the DMC formation step which is related to the affinity of CO2 and relatively strong acidities

3.2.2 Metal-Based Supported Materials

Bimetallic based supported materials have been widely investigated and applied in several catalytic reactions [82, 83]. Several supported materials have been prepared and crucial factors affect the DMC synthesis. Since the support is not merely a carrier but also can significantly contribute to the activity of the catalyst. CuCl2 supported on activated carbon (AC), a conventional catalyst in the oxy-carbonylation of methanol, was applied for the direct DMC synthesis. The reaction was carried out at 100–140 °C and 1–1.4 MPa. A selectivity of 91% for DMC was reached, producing methyl formate and dimethyl ether as side products [84]. Moreover, comparable activities of a Cu–Ni catalyst supported on activated carbon, thermally expanded graphite, multi-walled carbon nanotubes, and graphene nanotubes (GNS), at 120 °C and 1.2 MPa was reported. The catalyst supported on GNS showed the highest activity with a selectivity of 83%, which increases to 90% for temperatures below 353 K [85].

The Cu–Ni alloy supported on molecular sieve were investigated as well [86]. Taking advantage of molecular sieves such as high specific surface area, strong absorbability, good thermal and favorable hydrothermal stability may significantly contribute to the activity of the catalyst. Moreover, the ability to remove water from the reaction system is an additional advantage when using molecular sieve supported catalysts. Obviously, a Cu–Ni alloy metal affects the acidity and basicity and subsequently activate methanol to methoxy species before reacting with CO2 species. Later on, a termetallic catalyst allowed the possibility of systematically altering the size and/or the electronic structure of the synthesized catalyst. The V-doped Cu–Ni/AC catalyst was synthesized and showed an effective improvement of the catalytic performance and selectivity [87]. The V-doping enhanced the metal dispersion of the active metal particles (Cu and Ni) on the surface of the support. Moreover, the reduction of active metals to lower valent species was inhibited due to V incorporation and played a crucial role in the catalyst stability. Another study on the effect of the support material was performed using Rh with different conventional supports such as Al2O3, SiO2, ZSM-5 [88]. A high conversion but lower selectivity on Rh/ZSM-5 over Rh/SiO2 was observed. The support influences the surface stabilization of methoxy groups in the area of adsorbed CO2 which greatly affects the DMC selectivity as DMC formation occurs via the adsorbed CO2 with methoxy species to form a methoxy carbonate over the catalyst surface. The high cost of commercial support materials, low activity and short longevity of the existing catalysts are still major concerns before the catalysts can be applied on a large scale or industrial level. Carbonaceous materials have been used as supporting materials and even directly used as a catalyst [89]. Thermally expanded graphite (TEG) which is a kind of wormlike material obtained from the vaporization of the graphite intercalation compounds (GICs), was applied as support for Cu–Ni bimetallic catalysts [90]. Expansion of TEG along the crystallographic c-axis resulted in an increase of the surface area and a high surface activity. The multifunctional inorganic material TEG anchored and dispersed the Cu–Ni alloy leading to a higher surface area of active metals. Cerium oxide with supporting materials made by template-precipitation to enhance the catalytic performance based on the cerium metal was reported as well [91]. The catalyst characterization revealed that the relationship between acid–base sites and the composite catalyst is key for the catalytic activity. Temperature programmed desorption (CO2−, NH3-TPD) demonstrated a large amount of acid and basic sites on CeO2-4A (4A-molecular sieves) over CeO2 and CeO2–SiO2 which causes the high activity of the catalyst. Both acid and basic sites are needed to produce DMC. The basic sites are responsible for producing the methoxy groups and for the activation of carbon dioxide generating the methoxy carbonate anion that will react with the methyl group formed by the acid sites to finally produce DMC [44, 92, 93]. Lee et al. obtained 1.2% and 2.3% of DMC after 3 h using H3PW12O40 and Ga2O3, respectively, supported on a mixture composed by CexZr1−xO2, at 170 °C and 6 MPa. A linear relation between the activity and the amount of acidity and basicity was observed. The maximum catalyst activity was reached using 5Ga2O3/Ce0.6Zr0.4O2, which also showed the highest basicity and acidity. All catalysts were calcinated at 500 °C for 3 h [92, 94].

3.2.3 Metal–Organic Frameworks

Porous coordination polymers (PCPs), also well-known as metal–organic frameworks (MOFs), constructed from metal ion/cluster nodes bridging with organic linkers and formed framework networks of two or, most typically, three dimension [95, 96, 97]. MOFs are mostly crystalline materials and their crystallinity is mostly determined by crystal analysis such as single crystal, synchrotron, and X-ray diffraction analysis (XRD), etc. The tailored structures, in metal and organic linker, make a distinct advantage of MOFs over other materials. Moreover, the well-defined framework contains voids and porosities which have a potential for several different applications. Additionally, the post-synthetic modifications (PSMs) via functionalizing the organic linker or metal modes after MOF synthesis to control their pore environment can also enhance the performance of their application. MOF catalysis is one of the most attractive applications of which the progress was reviewed extensively during recent years [98, 99, 100]. Among MOF materials, the stable MOF, UiO-66, with zirconium (Zr6+) cluster bridging with 12-linkers (terephthalic acid, BDC), was applied as a catalyst for the direct DMC synthesis from methanol and CO2 [101]. Moreover, the unique properties of this material and the high porosity have the ability to adsorb more CO2 over the metal oxide catalyst and increase the concentration of CO2 around the catalytic active centers [102, 103, 104]. The Lewis acid sites deriving from zirconium metals in UiO-66 act as active sites for the catalytic production of DMC [105]. The open sites in the MOFs (coordinative unsaturated sites) are very important since they act as active sites for the catalysis and the activity relatively increases with the number of defects or missing linkers. The influence of the number of defects in UiO-66 modulated by using trifluoroacetic acid (TFA) was recently reported [106]. The catalytic activity obtained exhibits a similar trend as the number of active sites (Lewis acid site, Lewis basic site, and terminal hydroxyl). Furthermore, due to the high porosity and uniform properties of MOFs, they could act as catalysts themselves but also serve as hosts or support materials to embed active catalyst species. The zeolitic imidazolate framework-8 (ZIF-8) supported bimetallic Cu–Ni were synthesized via wet impregnation and directly applied for the DMC synthesis [107]. The highest DMC yield (6.39%) and the highest MeOH conversion (12.79%) were achieved at 20 bar of CO2, 110 °C and 12 h using 0.7 g of 5% Cu–Ni/ZIF-8 catalyst. Under the optimized conditions, the catalyst was able to retain its catalytic performance up to 4 regeneration cycles. The high-resolution XPS spectra revealed unreduced species (Cu and Ni) which are related to the active sites [108]. However, the fraction of CuO species present in the spent catalyst increases after each cycle and suggests that partial oxidization of copper occurs during the reaction. A similar phenomenon is observed for nickel species as the fraction of NiO in the spent catalyst increases.

4 Perspective and Outlooks

An overview of the catalytic performance achieved for the DCM synthesis, including homogeneous and heterogeneous catalysts as well as the addition of co-catalyst, and reaction conditions are summarized in Table 3, 4, and 5. In general, due to the high oxidation state of CO2 molecules related to their thermodynamic stability, the utilization of CO2 in reactions requires critical conditions and high-energy consumption. Although, the simulation revealed that thermodynamics play a role in the DMC synthesis, however, the decrease in DMC selectivity was also experimentally observed at the high reaction temperature. The decomposition of DMC molecules is the main reason for the selectivity decrease. Therefore, a catalyst with excellent performance under milder optimized reaction conditions is of primary importance. Several catalysts showed advantages and disadvantages towards the performance for the direct DMC synthesis. The acid and bases sites are mostly reported to actively catalyze the reaction. The novel design of catalyst that has both active sites could enhance the catalytic performance. As mentioned before, water formation is one of the main drawbacks of the carbonylation of methanol. The removal of water from the reaction via the addition of dehydrating agents is a suitable strategy to shift the reaction equilibrium toward the right side without interfering in the reaction mechanism. Despite the attempts made to improve this process, using more efficient dehydrating agents (such as inorganic materials: zeolites, etc.) or a dehydration unit (such as membrane reactor, etc.), could show significant improvements in obtaining higher conversions. However, it is difficult to conclude which one is the best performing catalyst since this depends on different factors such as economic, environment, operational as well as safety and human health impact. Future challenges include the development of non-halogen containing catalysts, development of immobilized or solid catalysts to be applied in flow reactor processes, utilization of new reaction media such as supercritical CO2 or ionic liquids.
Table 3

Overview of reported homogeneous catalysts with the reaction conditions for the dimethyl carbonate synthesis using a batch reactor

Catalyst

Reaction condition

Catalyst activity

Refs.

Conversion-%

Selectivity-%

Yield-%

[bmim][Cl]

Temperature: 170 °C,

PCO2: 40 bar,

MeOH: 10 mL,

Catalyst weight: 2.5 mmol,

Co-catalyst (2,2-dimethoxy propane): 25 mmol,

Time: 24 h

7.46

53.0

/

[109]

[bmim][BF4]

7.43

81.3

/

 

[bmim][PF6]

7.19

47.0

/

 

[emim][BF4]

9.22

83.3

/

 

[emim][Tf2N]

8.98

43.0

/

 

[mbmim][Tf2N]

6.81

35.1

/

 

[dmbmim][Tf2 N]

6.65

33.6

/

 

[bpy][Cl]

7.73

53.4

/

 

[bpy][BF4]

7.52

60.7

/

 

[bpy][PF6]

7.57

41.4

/

 

[bpy][Tf2N]

7.43

34.5

/

 

[epy][BF4]

7.65

63.7

/

 

[epy][Tf2N]

9.35

9.3

/

 

[dmbpy][Tf2N]

6.78

28.8

/

 

[GLY(mim)3][OMs]3

Temperature: 130 °C,

PCO2 :75 bar,

MeOH: 616 mmol,

Catalyst weight: 5 mmol,

Time: 6 h

22.0

45.8

6.6

[110]

[GLY(mim)3][NTf2]3

22.9

51.0

10.0

 

[GLY(mim)3][Br]3

20.0

42.1

8.4

 

[GLY(mim)3][OMs]3/DBU

27.9

73.0

20.0

 

[GLY(mim)3][NTf2]3/DBU

37.1

94.0

35.0

 

[GLY(mim)3][Br]3/DBU

31.9

82.0

26.0

 

[C1C4Im][HCO3] + CsCO3

Temperature: 25 °C,

PCO2 :10 bar, Time: 24 h,

Catalyst weight: 5 mmol,

Co-Catalyst: 5 mmol (base salt)

82.0

94.0

/

[111]

[C1C4Im][HCO3] + KHCO3

24.0

99.0

/

 

[C1C6Im][HCO3] + CsCO3

47.0

99.0

/

 
  

Conversion-%

DMC (mmol)

Selectivity-%

 

CH

Temperature: 140 °C,

PCO2: 30 bar,

MeOH: 625 mmol,

Catalyst weight: 30.8 mmol,

Time: 3 h

0.6

1.63

96

[41]

BMDH

0.54

1.59,

96

 

MTH

0.62

1.83

97

 

THH

0.2

0.61

98

 

BzMDH

1.48

4.48

99

 

BzTH

0.83

2.47

98

 

BzMDH/SBA-15

0.13

0.41

99

 

BzMDH/CNT

0.15

1.46

99

 

BzMDH/CaO

0.96

2.90

99

 

HIMH 0.49

0.18

0.18

99

 

BmimOH

0.09

/

/

 

CH

Temperature: 140 °C,

PCO2: 30 bar,

MeOH: 625 mmol,

Catalyst weight: 0.066 mmol,

Time: 6 h

0.6

1.63

95

[40]

EmimOH

0.1

0.31

87

 

EtmimOH

0.2

0.62

77

 

CH + CaO

0.5

1.56

93

 

CH + CH3I

2.7

8.19

99

 

Triorganotin(IV)

Temperature: 150 °C,

PCO2: 200 bar,

MeOH: 20 ml,

Catalyst weight: 1.1 mmol,

Time: 24 h

 

1.7

(TON 1.5)

/

[112]

n-Bu2Sn(OCH3)2

Temperature: 150 °C,

PCO2: 200 bar, 0.82 mol

MeOH: 0.5 mol,

Catalyst weight: 4 mmol,

Time: 15 h

/

3.75

/

[48]

Table 4

Dimethyl carbonate synthesis by variance heterogeneous catalyst with variance reaction condition in batch reactor

Catalyst

Reaction condition

Catalyst activity

Refs.

Conversion-%

DMC (mmol)

Selectivity-%

ZrO2–MgO

Temperature: 180 °C,

PCO2: 45 bar,

MeOH: 695 mmol,

Catalyst weight: 1 g,

Co-Catalyst (butylene oxide): 21.3 mmol

/

0.7

/

[113]

  

Conversion-%

Selectivity-%

Yield-%

 

ZrO2–MgO +[C4-mim][MeO]

Temperature: 120 °C,

PCO2: 450 bar,

MeOH: 197 mmol,

Catalyst weight: 0.5 g

Co-Catalyst (IL): 24 g,

Time: 9 h

12.1

90

/

[42]

ZrO2–MgO + [C2-mim][MeO]

12.6

89

/

ZrO2–MgO +[BA][MeO]

10.5

69

/

ZrO2–MgO + CH3ONa

5.5

71

/

  

Conversion-%

DMC (mmol)

Selectivity-%

 

ZrO2

Temperature: 110 °C,

PCO2: 50 bar,

MeOH: 192 mmol,

Catalyst weight: 1 g,

Time: 2 h

/

0.12

100

[58]

ZrO2/0.33%CeO2

/

0.73

100

CeO2

 

Non-active

 

CeO2

Temperature: 140 °C,

PCO2: 68 bar,

Catalyst weight: 0.2 g,

Time: 2 h

0.48

11.0

/

[63]

Zr0.05Ce

0.58

13.5

/

Zr0.1Ce

0.60

/

14.0

Zr0.2Ce

054

/

12.5

Zr0.3Ce

0.50

/

11.5

ZrO2

0.80

/

2.0

Ce0.4Zr0.6O2

Temperature: 170 °C,

PCO2 :75 bar,

MeOH: 123 mmol,

Catalyst weight: 0.7 g,

Time: 3 h

0.32

0.7

/

 

Gd–Ce0.4Zr0.6O2

1.13

0.7

/

CeO2 nanorod

Temperature: 120 °C,

PCO2 :50 bar,

MeOH: 20 mL,

Catalyst weight: 0.2 g,

Time: 5 h

/

0.64

/

[69]

Ti0.04Ce0.96O2

5.4

0.94

83.0

ZrO2

Temperature: 110 °C,

PCO2 :50 bar,

MeOH: 12 g,

Catalyst weight: 1 g,

Time: 4 h

/

0.12

100

[74]

Fe0.5Zr0.7Oy

/

0.35

100

Fe0.7Zr0.7Oy

/

0.44

100

Fe0.9Zr0.1Oy

/

0.28

100

Fe2O3

/

0.04

100

Ce1-Ca1

Temperature: 120 °C,

PCO2 :150 bar,

MeOH: 294 mmol,

Catalyst weight: 1.25 g,

Time: 24 h

2.3

2.96

/

[76]

Ce1–Ca1.5

Temperature: 140 °C,

PCO2 :30 bar,

MeOH: 35 mL,

Catalyst weight: 1 g,

Time: 3 h.

/

2.47

/

[77]

Cu–CeO2

Temperature: 120 °C,

PCO2 :130 bar,

MeOH: 134 mmol,

Catalyst weight: 0.1 g,

Time: 4 h

0.6

0.4

/

[114]

0.02% Cu–CeO2

Temperature: 140 °C,

PCO2 :50 bar,

MeOH: 15 mL,

Catalyst weight: 0.1 g,

Time: 3 h

1.6

2.3

100

[115]

0.02% Cu–CeO2 (2-CP)

5.0

14.5

100

 

0.02% Cu–CeO2 (MTCL)

14.0

35.7

80

 

Ce-Zr@Graphene

Temperature: 110 °C,

PCO2 :275 bar,

MeOH: 10 g,

Catalyst weight: 10% w/w,

Time: 16 h

58.0 (Yield 33%)

/

/

[116]

Sn@SBA-15

Temperature: 150 °C,

PCO2 :200 bar,

MeOH: 0.5 mol,

Catalyst weight: 0.1 g,

Time: 15 h

/

0.32

/

[117]

Sn@SBA-15(Treatment)

/

0.32

/

Sn@SBA-CH3

/

0.62

/

Sn@SBA-CH3(Treatment)

/

0.61

/

ZnCl2@Ch-g-Acrylamide

Temperature: 150 °C,

PCO2 :200 bar,

MeOH: 0.5 mol,

Catalyst weight: 0.1 g,

Time: 15 h

5.3

/

98.0

[118]

ZnCl2@Ch-g-Polyaniline

3.1

/

92.4

ZnCl2@Ch-g-PEI

23.8

/

99.0

ZnCl2@Ch-g-Allylamine

11.0

/

99.0

UiO-66

Temperature: 120 °C,

MeOH: 200 mmol,

Catalyst weight: 0.5 g,

Time: 1 h

0.03

/

0.015

[106]

UiO-66-6%TFA

0.068

/

0.030

 

UiO-66-12%TFA

0.132

/

0.066

 

UiO-66-18%TFA

0.15

/

0.075

 

UiO-66-24%TFA

0.168

/

0.084

 

ZrO2

0.03

/

0.015

 

CrO2

0.142

/

0.071

 
Table 5

Dimethyl carbonate synthesis by variance heterogeneous catalyst with variance reaction condition in flow reactor

Catalyst

Reaction condition

Catalyst activity

Refs.

Cu–Ni@Molecular sieve

Temperature: 120 °C,

PCO2: 11 bar,

GSHV: 510 h−1

Yield 0.7 mmol

[113]

  

Catalyst activity

 

Conversion-%

Selectivity-%

Yield-%

CeO2

Temperature: 120 °C,

PCO2: 6 bar,

GSHV: 300 h−1,

Catalyst weight: 1 g

1.78

83.0

1.48

[91]

CeO2–SiO2

2.00

86.0

1.80

CeO2-4A

3.97

8.0

3.23

Ce0.1Ti0.9O2

Temperature: 170 °C,

PCO2: 50 bar,

Catalyst weight: 1 g

4.00

55.0

2.30

[66]

H3PW12O40/Ce0.1Ti0.9O2

5.50

91.4

5.00

Fe–Cu

Temperature: 120 °C,

PCO2: 6 bar,

GSHV: 360 h−1,

Catalyst weight: 2 g

4.72

86.5

4.08

[119]

1%Mo@Fe-Cu

5.59

90.4

5.05

2.5%Mo@Fe-Cu

6.99

87.7

6.13

5.5%Mo@Fe-Cu

5.87

84.6

4.95

1%La@CeO2

Temperature: 120 °C,

PCO2: 30 bar,

GSHV: 360 h−1,

Catalyst weight: 0.3 g

80.0

94.5

/

[120]

1%Gd@CeO3

85.0

99.0

/

1%Pr@CeO4

82.0

98.0

/

5% Rh/Al2O3

Temperature: 120 °C,

Catalyst weight: 0.5 g

/

98.0

5.4

[88]

5%Rh/SiO2

/

40.0

16.7

5%Rh/ZSM-5

/

60.0

24.9

Cu@Activated carbon

Temperature: 120 °C,

PCO2: 12 bar,

Catalyst weight: 3 g

/

90.1

4.8

[84]

Cu-Ni@TEG carbon

Temperature: 100 °C,

PCO2: 12 bar,

Catalyst weight: 1 g

4.97

89.3

 

[90]

The investigation using continuous flow reaction conditions are new opportunities in heterogeneous catalysis since in general this reaction was performed in batch processes and thus limited by the equilibrium due to the presence of water. Combining a membrane reactor for separation could instantly and continuously remove products from the reaction mixture. Different types of membranes need to be investigated in a membrane reactor and could improve the methanol conversion drastically in comparison with the use of conventional catalytic reactors. Besides the use of reactants as dehydrating agents, the authors believe that the development of a process intensification unit, coupling reaction, and water separation, would also be an interesting and potential alternative.

In general, harsh reaction conditions of temperature and pressure are required for this reaction. Possible approaches for the CO2 transformation reaction can be: (1) use of a high-energy substrate such as hydrogen, active compounds or organometallics; (2) aiming at low energy molecules as target product such as organic carbonates, (3) designing an equilibrium process shifted towards the product side via withdrawal of a side product, (4) applying an additional energy source to perform the transformation, e.g. light, electricity, etc.

5 Conclusion

DMC can be synthesized directly from methanol and CO2. However, the yield of DMC is low because of the thermodynamic limitations of the reaction. Acid/basic sites are mostly reported to be the active sites for the reaction. For both liquid and gas phases, the DMC selectivity is more strongly dependent on the temperature. The low reaction temperature is more favorable for DMC formation. Moreover, high temperatures decrease both the conversion of methanol and the selectivity to DMC. The decrease of DMC selectivity might be due to its decomposition at high temperatures. However, a low temperature will not be sufficient to activate CO2 molecules which is required for the direct synthesis of DMC. The design of highly active new catalysts to promote the reaction should be a continuous development task in research. Still, the review aims at guiding researchers with the ideas presented in this manuscript to develop potential catalytic materials that allow the DMC synthesis to be carried out under milder conditions and possible on a larger scale.

Notes

Acknowledgements

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 (No. 21850410449). F.V. acknowledges the support from Tomsk Polytechnic University Competitiveness Enhancement Program Grant (VIU-2019).

Compliance with Ethical Standards

Conflict of interest

On behalf of all authors, the corresponding author states that there is no conflict of interest.

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Copyright information

© The Tunisian Chemical Society and Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.Laboratory of Organometallics, Catalysis and Ordered Materials, State Key Laboratory of Advanced Technology for Materials Synthesis and ProcessingWuhan University of TechnologyWuhanChina
  2. 2.National Research Tomsk Polytechnic UniversityTomskRussian Federation
  3. 3.Department of Chemistry, College of Arts and SciencesKhalifa UniversityAbu DhabiUAE
  4. 4.Ghent University Global Campus, SongdoIncheonKorea
  5. 5.Chemistry Department, Faculty of ScienceKing Abdulaziz UniversityJiddahSaudi Arabia

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