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www.nature.com/scientificreports/ Figure 4. TEM images of (a) MNPs, (b) SMNPs, (c) Cu-ABF@ASMNPs catalyst, (d) FE-SEM image of Cu-ABF@ASMNPs and (e) SAED pattern of MNPs. (1,8-Diazabicyclo(5.4.0)undec-7-ene), PPh3 (Triphenylphosphine), DMAP [4-(dimethylamino) pyridine], Et3N (Triethylamine) and TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene) could activate CO2 at atmospheric pressure41,78–81. As listed in Fig. 8, the reaction did not occur in absence of both the catalyst and base (entry 1). In presence of DBU only, 2% yield of styrene carbonate was observed when 4 mol% of DBU was used (entry 2) and with increase in amount of DBU to 12 mol%, improvement in yield was observed (entry 3). When the catalyst (Cu-ABF@ ASMNPs) was used alone in absence of DBU, it was found to be almost inactive (entry 4) and this result proves the importance of DBU as CO2 activator. However, the combination of DBU and the catalyst afforded 90% yield of the desired product (entry 5) and this observation confirms the significance of our copper nanocatalyst. Under the same reaction conditions, different organic bases were employed and DBU was found to be the best organic base than TBD, DMAP, Et3N and PPh3 for the activation of CO2 and provided the highest yield of styrene carbonate (entries 5–9). Next, we studied the effect of solvent in the cycloaddition reaction and we observed that among various solvents including DMF, DMSO, CH3CN, NMP and toluene, DMF appeared to be the best (entries 5, 10–13). When, the reaction was carried out under neat condition, to our surprise better yield of the product was found. Hence, it is confirmed that solvent does not play any significant role. Further, the catalytic amount was varied and 50 mg of the catalyst was found to be optimum to give the highest yield of styrene carbonate (entries 14–16). When the precursor materials (namely ABF@ASMNPs, ASMNPs and MNPs) were used, no significant conversions of the styrene oxide were observed (Fig. 9, entries 1–3). The presence of copper-based source is extremely significant to catalyse the cycloaddition reaction of epoxide with CO2 (entries 4–6). The highest per- centage was obtained in the case of Cu-ABF@ASMNPs, demonstrating the efficiency of the copper nanocatalyst in the cycloaddition reaction (entry 7). Under the optimised reaction conditions, this newly developed catalyst was then examined for other substrates as shown in Fig. 10. The results demonstrated that different epoxides converted to corresponding cyclic carbonates under mild conditions in high to excellent yields. The Cu-ABF@ ASMNPs nanocatalyst also showed promising results in terms of mild reaction condition in comparison with the literature precedents (Table S1). SCientifiC RepoRts | (2018) 8:1901 | DOI:10.1038/s41598-018-19551-3 5PDF Image | copper-based magnetic nanocatalyst for the fixation of carbon dioxide
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