Porous Hexacyanometallate(III) Complexes as Catalysts in the Ring-Opening Copolymerization of CO2 and Propylene Oxide
Abstract
:1. Introduction
2. Results
2.1. Porous Hexacyanometallates(III) Characterization
2.1.1. Crystal and Electronic Structure
2.1.2. Thermal Stability, Degree of Hydration, and Dehydration Process
2.1.3. Chemical Composition
2.1.4. Morphology and Textural Properties
2.1.5. Density of Coordinatively Unsaturated Metal Sites (CUMSs)
2.2. Catalytic Activity Tests
Comparison of the Performance of the Studied Compounds with Other Cyanometallate Catalysts for CO2/PO Copolymerization
3. Materials and Methods
3.1. Materials
3.2. Preparation of Porous Hexacyanometallates(III)
3.3. CO2/PO Copolymerization Procedure
3.4. Characterization
3.4.1. Porous Hexacyanometallate(III) Characterization
3.4.2. Polymer Characterization
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Compound | δ(MII-CN) | ν(MII-C) | ν(CN) | δ(HOH) | ν(H2O) |
---|---|---|---|---|---|
[Co(CN)6]3− | 416 s | 565 m | 2125 s | - | - |
[Fe(CN)6]3− | 417 m | 511 m, 583 w | 2118 s | - | - |
Ni-Co | - | 461 m | 2141 m, 2183 s | 1609; 1634 (sh) | 3404; 3646 (br, s) |
Co-Co | - | 457 m | 2176 s | 1609; 1634 (sh) | 3409; 3646 (br, s) |
Fe-Co | - | 469 m | 2175 s | 1607; 1639 (sh) | 3415; 3646 (br, s) |
Ni-Fe | 432 sh, 439 w | 541 w, 594 w | 2098 m, 2167 s | 1609; 1662 (sh) | 3396; 3646 (br, s) |
Co-Fe | 431 w, 440 sh | 540 w, 593 w | 2116 s, 2159 m | 1609; 1651 (sh) | 3404;3641 (br, s) |
Fe-Fe | 501 m, 512 sh | 603 w | 2080 s | 1606; 1638 (sh) | 3369; 3595; 3625 (br, br, s) |
Compound | Cell Edge (Å) | V (Å3) | Crystallite Size (nm) | Strain (ε) | |
---|---|---|---|---|---|
D-S | W-H | ||||
Ni-Co | 10.07 | 1020 | 9.4 | 13.2 | 0.00220 |
Co-Co | 10.16 | 1049 | 21.5 | 29.4 | 0.00093 |
Fe-Co | 10.17 | 1051 | 26.2 | 33.5 | 0.00061 |
Ni-Fe | 10.15 | 1047 | 8.3 | 11.4 | 0.00243 |
Co-Fe | 10.22 | 1068 | 27.6 | 43.6 | 0.00103 |
Fe-Fe | 10.16 | 1049 | 34.6 | 44.1 | 0.00049 |
Compound | H2O, wt % | Dehydration Temp. (°C) * | Decomposition Temp. (°C) * | ||
---|---|---|---|---|---|
N2 | Air | N2 | Air | ||
Ni-Co | 29.30 | 145 | 150 | 490 | 310 |
Co-Co | 29.71 | 110 | 115 | 515 | 265 |
Fe-Co | 25.15 | 94 | 96 | 495 | 290 |
Ni-Fe | 29.73 | 140 | 150 | 540 | 305 |
Co-Fe | 30.83 | 105 | 108 | 500 | 255 |
Fe-Fe | 22.46 | 107 | 110 | 525 | 225 |
Compound | Cell Contraction (%) | Cell Edge after Dehydration (Å) | Cell Volume Reduction (%) | Cell Volume after Dehydration (Å3) |
---|---|---|---|---|
Ni-Co | 1.7 | 9.89 | 5.1 | 968 |
Co-Co | 2.0 | 9.96 | 5.7 | 989 |
Fe-Co | 1.2 | 10.05 | 3.5 | 1015 |
Ni-Fe | 1.8 | 9.97 | 5.4 | 991 |
Co-Fe | 2.4 | 9.98 | 7.0 | 993 |
Fe-Fe | 1.4 | 10.02 | 4.1 | 1006 |
Compound | XRF (wt%) | T/M (at./at.) | EA (wt%) | Estimated Catalyst Formulation | ||||
---|---|---|---|---|---|---|---|---|
T | M | K | Cl | C | N | |||
Ni-Co | 24.5 | 12.3 | 0.2 | 1.9 | 2.0 | 14.4 | 17.6 | Ni1.99[Co(CN)6.01]·7.78 H2O *·0.26 Cl−·0.03 K+ |
Co-Co | MI=MII: 38.3 | 0.4 | 1.8 | - | 14.4 | 16.2 | - | |
Fe-Co | 21.8 | 12.8 | 0.1 | 1.4 | 1.8 | 17.3 | 20.1 | Fe1.81[Co(CN)6.45]·6.41H2O *·0.19 Cl−·0.01 K+ |
Ni-Fe | 24.8 | 11.8 | 0.2 | 1.5 | 2.0 | 14.3 | 17.8 | Ni2.01[Fe(CN)6.02]·7.80 H2O *·0.19 Cl−·0.02 K+ |
Co-Fe | 23.5 | 13.0 | 0.6 | 1.1 | 1.7 | 15.5 | 17.3 | Co1.72[Fe(CN)5.30]·6.95 H2O *·0.14 Cl−·0.06 K+ |
Fe-Fe | MI=MII: 36.6 | 1.5 | 0.9 | - | 16.8 | 19.6 | - |
Compound | SBET a (m2/g) | Sext b (m2/g) | Surface Area Contributed by Micropores (%) |
---|---|---|---|
Ni-Co | 373 | - | 100 |
Co-Co | 801 | 155 | 81 |
Fe-Co | 757 | 156 | 79 |
Ni-Fe | 161 | 4 | 98 |
Co-Fe | 624 | 95 | 85 |
Fe-Fe | 213 | 75 | 65 |
Compound | Vt a (cm3/g) | Vmicro (cm3/g) | Pore Volume Contributed by Micropores e (%) | ||
---|---|---|---|---|---|
Vm(BET) = Vmicro + Vm(ext) b | DA-Plot c | t-Plot d | |||
Ni-Co | 0.146 | 0.132 | 0.146 | 0.144 | 97 |
Co-Co | 0.496 | 0.230 | 0.325 | 0.258 | 55 |
Fe-Co | 0.680 | 0.214 | 0.309 | 0.263 | 39 |
Ni-Fe | 0.066 | 0.056 | 0.065 | 0.062 | 92 |
Co-Fe | 0.590 | 0.188 | 0.267 | 0.216 | 38 |
Fe-Fe | 0.201 | 0.049 | 0.097 | 0.068 | 36 |
Compound | Total Acidity a (μmol NH3 g−1) | Acid Sites Density a (μmol NH3 m−2) |
---|---|---|
Ni-Co | 1880 | 5.0 |
Co-Co | 2780 | 3.5 |
Fe-Co | 2010 | 2.7 |
Ni-Fe | 1960 | 12.2 |
Co-Fe | 3780 | 6.1 |
Fe-Fe | 1550 | 7.3 |
Compound | Yield b (g) | TOF c | FCU d mol (%) | FCO2 e (wt%) | WPC f (wt%) | SCO2 g (%) | SPO h (%) | RPEC (%) | Mw (g mol−1) | ĐM |
---|---|---|---|---|---|---|---|---|---|---|
Ni-Co | 3.2 | 4 | 22.3 | 14.4 | 0.4 | 98.9 | 99.7 | 79.5 | 11,800 | 10.5 |
Co-Co | 18.9 | 23 | 20.0 | 13.1 | 4.2 | 87.4 | 97.2 | 71.9 | 68,600 | 4.1 |
Fe-Co | 14.8 | 18 | 16.3 | 11.0 | 8.4 | 73.6 | 94.5 | 75.1 | 85,400 | 6.3 |
Ni-Fe | 3.0 | 4 | 24.0 | 15.3 | 0.6 | 98.4 | 99.6 | 73.9 | 11,700 | 15.8 |
Co-Fe | 11.6 | 12 | 33.5 | 20.2 | 13.3 | 75.4 | 90.2 | 66.0 | 50,000 | 5.9 |
Fe-Fe | 6.0 | 7 | 17.3 | 11.6 | 43.1 | 26.2 | 67.2 | 83.3 | 6000 | 8.4 |
Catalyst Formulation | Time (h) | PO/Cat. (g/g) | P (bar) | T (°C) | TON a | TOF b | FCU (mol%) | WPC (wt%) | SCO2 (%) | Mw (g mol−1) | ĐM | Ref |
---|---|---|---|---|---|---|---|---|---|---|---|---|
Ni3[Co(CN)6]2 | 24 | 400 | 20 | 90 | 86 | 4 | 22 | 0.4 | 99 | 11,800 | 10.5 | - |
Co3[Co(CN)6]2 | 24 | 400 | 20 | 90 | 544 | 23 | 20 | 4.2 | 87 | 68,600 | 4.1 | - |
Fe3[Co(CN)6]2 | 24 | 400 | 20 | 90 | 428 | 18 | 16 | 8.4 | 74 | 85,400 | 6.3 | - |
Ni3[Fe(CN)6]2 | 24 | 400 | 20 | 90 | 84 | 4 | 15 | 0.6 | 98 | 11,700 | 15.8 | - |
Co3[Fe(CN)6]2 | 24 | 400 | 20 | 90 | 296 | 12 | 20 | 13.3 | 75 | 50,000 | 5.9 | - |
Fe4[Fe(CN)6]3 | 24 | 400 | 20 | 90 | 162 | 7 | 17 | 43.1 | 26 | 6000 | 8.4 | - |
Zn3[Co(CN)6]2 | 10 | 42,000 | 38 | 90 | 64,414 | 6441 | 13 | 4.4 | 82 | 10,800 | 1.8 | [103] |
Zn3[Fe(CN)6]2 c | 10 | 4611 | 50 | 110 | 137 | 14 | 15 | 62.5 | 12 | 2160 | n.a. | [50] |
Zn3[Cr(CN)6]2 c | 10 | 4611 | 50 | 140 | 334 | 33 | 10 | 36.6 | 22 | 1350 | n.a. | [50] |
Zn[Cd(CN)4] c | 10 | 4611 | 50 | 130 | 35 | 4 | 2 | 6.5 | 33 | n.a. | n.a. | [50] |
Zn2[Mo(CN)8] c | 10 | 4611 | 50 | 130 | 196 | 20 | 14 | 16.5 | 53 | 1420 | n.a. | [50] |
Zn2[Fe(CN)6]2 c | 10 | 4611 | 50 | 110 | 233 | 23 | 5 | 77.8 | 2 | n.a. | n.a. | [50] |
Zn[Ni(CN)4] | 20 | 553 | 50 | 110 | 210 | 11 | 62 | 6.6 | 91 | 2360 | 1.8 | [91] |
Co[Ni(CN)4]2 | 1 | 664 | 54.4 | 90 | 1510 | 1510 | 27 | - | 100 | 526,400 | 2.8 | [56] |
Co[Pd(CN)4]2 | 1 | 546 | 54.4 | 90 | 18 | 18 | 43 | - | 100 | 92,160 | 3.6 | [56] |
Co[Pt(CN)4]2 | 1 | 411 | 54.4 | 90 | 13 | 13 | 44 | - | 100 | 103,230 | 3.7 | [56] |
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Penche, G.; González-Velasco, J.R.; González-Marcos, M.P. Porous Hexacyanometallate(III) Complexes as Catalysts in the Ring-Opening Copolymerization of CO2 and Propylene Oxide. Catalysts 2021, 11, 1450. https://doi.org/10.3390/catal11121450
Penche G, González-Velasco JR, González-Marcos MP. Porous Hexacyanometallate(III) Complexes as Catalysts in the Ring-Opening Copolymerization of CO2 and Propylene Oxide. Catalysts. 2021; 11(12):1450. https://doi.org/10.3390/catal11121450
Chicago/Turabian StylePenche, Guillermo, Juan R. González-Velasco, and M. Pilar González-Marcos. 2021. "Porous Hexacyanometallate(III) Complexes as Catalysts in the Ring-Opening Copolymerization of CO2 and Propylene Oxide" Catalysts 11, no. 12: 1450. https://doi.org/10.3390/catal11121450