On the mechanism of CO2 electro-cycloaddition to propylene oxides

Gallardo-Fuentes, Sebastián; Contreras, Renato; Isaacs, Mauricio; Honores, Jessica; Quezada, Diego; Landaeta, Esteban; Ormazábal‐Toledo, Rodrigo

doi:10.1016/j.jcou.2016.06.007

Cited by 27 publications

(33 citation statements)

References 44 publications

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“…The XRD patterns of both Zr/ZIF-8 and recycled Zr/ZIF-8 catalysts are identical as shown in Figure 4, confirming that Zr/ZIF-8 has high crystal stability under the normal reaction conditions. These results are in agreement with simulated patterns reported in other literature [25][26][27][28]. The decrease in peak intensity of these diffractions was also observed at (2θ = 28-35 • ) indicating the effect of excess doping of Zr into the ZIF-8 framework.…”

Section: Catalyst Characterizationsupporting

confidence: 92%

Comparison of Catalytic Activity of ZIF-8 and Zr/ZIF-8 for Greener Synthesis of Chloromethyl Ethylene Carbonate by CO2 Utilization

Olaniyan

Saha

2020

Energies

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The catalytic activity of both ZIF-8 and Zr/ZIF-8 has been investigated for the synthesis of chloromethyl ethylene carbonate (CMEC) using carbon dioxide (CO2) and epichlorohydrin (ECH) under solvent-free conditions. Published results from literature have highlighted the weak thermal, chemical, and mechanical stability of ZIF-8 catalyst, which has limited its large-scale industrial applications. The synthesis of novel Zr/ZIF-8 catalyst for cycloaddition reaction of ECH and CO2 to produce CMEC has provided a remarkable reinforcement to this weak functionality, which is a significant contribution to knowledge in the field of green and sustainable engineering. The enhancement in the catalytic activity of Zr in Zr/ZIF-8 can be attributed to the acidity/basicity characteristics of the catalyst. The comparison of the catalytic performance of the two catalysts has been drawn based on the effect of different reaction conditions such as temperature, CO2 pressure, catalyst loading, reaction time, stirring speed, and catalyst reusability studies. Zr/ZIF-8 has been assessed as a suitable heterogeneous catalyst outperforming the catalytic activities of ZIF-8 catalyst with respect to conversion of ECH, selectivity and yield of CMEC. At optimum conditions, the experimental results for direct synthesis of CMEC agree well with similar literature on Zr/MOF catalytic performance, where the conversion of ECH, selectivity and the yield of CMEC are 93%, 86%, and 76%, respectively.

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Section: Catalyst Characterizationsupporting

confidence: 92%

Comparison of Catalytic Activity of ZIF-8 and Zr/ZIF-8 for Greener Synthesis of Chloromethyl Ethylene Carbonate by CO2 Utilization

Olaniyan

Saha

2020

Energies

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“…The Cu(ND)/CP electrode remained its stable catalytic performance after three consecutive electrochemical reaction cycles (Figure S4c). The activity and stability of Cu(ND)/CP reached the best performance among the reported systems (Table S3), [7d,12b] suggesting the potential of the proposed system for practical applications. The small amount of byproduct was determined as 1‐phenyl‐1,2‐ethylene glycol by mass spectroscopy (Figure S5a) and IR (Figure S5b) characterization, which should be formed from the ring opening and subsequent hydration of SO [2a] …”

Section: Resultsmentioning

confidence: 87%

“…First, Cu 2+ with low electron density will coordinate with electron‐rich oxygen atoms from the reactant SO with the assistance of nucleophile TBAB (I), and then the Br − from TBAB attacks the methylene group to open the ring of SO forming metal‐bound alkoxides intermediates (II) [31] . CO 2 is chemically adsorbed on the surface of the catalyst (III) and is electrochemically activated (reduced) (IV) [12b,32] . Finally, the metal carbonate intermediate molecule is closed internally (V), [31a,33] and then it desorbed forming the target product SC (VI) [34]…”

Section: Resultsmentioning

confidence: 99%

Electrochemically Assisted Cycloaddition of Carbon Dioxide to Styrene Oxide on Copper/Carbon Hybrid Electrodes: Active Species and Reaction Mechanism

et al. 2022

Chemistry A European J

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A novel electrochemically assisted cycloaddition process is proposed, in which highly efficient coupling of CO 2 with styrene oxide (SO) can be achieved to form styrene carbonate (SC) as a high-value-added product. A series of Cu catalysts with different morphologies and chemical states were fabricated on carbon paper (CP) by using in-situ electrodeposition, and the sample with nano-dendrimer structure was found to exhibit a relatively high activity of 74.8 % SC yield with 92.7 % SO conversion under gentle reaction conditions, thus showing its potential for practical applications. The relatively high electrochemically active sur-face area and charge transfer ability of dendrimer-like Cu benefited the electrochemical reaction. In particular, the Cu 2 + species that were formed in situ during the reaction played a vital role in enhancing the activity and selectivity of the proposed Cu/CP hybrid catalyst. Cu 2 + atoms served as active sites that can not only electrochemically activate CO 2 but also facilitate the ring opening of SO. Mechanistic analysis suggested that the reaction followed electrochemical and liquid-phase heterogeneous paths, which provide a new green and sustainable route for efficient utilization of CO 2 resources for fine chemical electrosynthesis.

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“…The adequacy of the predicted models was validated by a number of statistical tools such as correlation coefficient (R 2 ), adjusted coefficient of determination (R 2 adj ), and the predicted coefficient of determination (R 2 pred ). The statistical significance of the predicted model was analyzed by (ANOVA) using a regression coefficient by conducting the Fisher's F-test at 95% confidence level [50]. Design Expert 11 software (Stat-Ease Inc., Minneapolis, MN, USA) was used for the design of experiment, regression, and graphical analysis.…”

Section: Discussionmentioning

confidence: 99%

Multiobjective Optimization for the Greener Synthesis of Chloromethyl Ethylene Carbonate by CO2 and Epichlorohydrin via Response Surface Methodology

Olaniyan

Saha

2020

Energies

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In this paper, a statistical analysis with response surface methodology (RSM) has been used to investigate and optimize process variables for the greener synthesis of chloromethyl ethylene carbonate (CMEC) by carbon dioxide (CO 2 ) and epichlorohydrin (ECH). Using the design expert software, a quadratic model was developed to study the interactions effect between four independent variables and the reaction responses. The adequacy of the model was validated by correlation between the experimental and predicted values of the responses using an analysis of variance (ANOVA) method. The proposed Box-Behnken design (BBD) method suggested 29 runs for data acquisition and modelling the response surface. The optimum reaction conditions of 353 K, 11 bar CO 2 pressure, and 12 h using fresh 12% (w/w) Zr/ZIF-8 catalyst loading produced 93% conversion of ECH and 68% yield of CMEC. It was concluded that the predicted and experimental values are in excellent agreement with ±1.55% and ±1.54% relative errors from experimental results for both the conversion of ECH and CMEC yield, respectively. Therefore, statistical modelling using RSM can be used as a reliable prediction technique for system optimization for greener synthesis of chloromethyl ethylene carbonate via CO 2 utilization.

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On the mechanism of CO2 electro-cycloaddition to propylene oxides

Cited by 27 publications

References 44 publications

Comparison of Catalytic Activity of ZIF-8 and Zr/ZIF-8 for Greener Synthesis of Chloromethyl Ethylene Carbonate by CO2 Utilization

Comparison of Catalytic Activity of ZIF-8 and Zr/ZIF-8 for Greener Synthesis of Chloromethyl Ethylene Carbonate by CO2 Utilization

Electrochemically Assisted Cycloaddition of Carbon Dioxide to Styrene Oxide on Copper/Carbon Hybrid Electrodes: Active Species and Reaction Mechanism

Multiobjective Optimization for the Greener Synthesis of Chloromethyl Ethylene Carbonate by CO2 and Epichlorohydrin via Response Surface Methodology

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