The Variety of Carbon-Metal Bonds inside Cu-ZSM-5 Zeolites: A Density Functional Theory Study
Abstract
:1. Introduction
2. Computational Section
3. Results and Discussion
3.1. ZSM-5 containing monocopper cation (Cu1–ZSM-5)
3.1.1. The small monocopper zeolite model
Free C2H2 | C2H2 on Cu1-zeolite | ||||
---|---|---|---|---|---|
Symmetry | Frequency | IR intensity a | Frequency | IR intensity a | |
C≡C stretch | Σg+ | 2001.4 | 0.00 | 1793.8 | 1.12 |
C–H stretch | Σg+ | 3400.0 | 0.00 | 3273.7 | 0.40 |
C–H stretch | Σu+ | 3300.5 | 1 | 3204.0 | 1 |
Free C2H4 | C2H4 on Cu1-zeolite | ||||
---|---|---|---|---|---|
Symmetry | Frequency | IR intensity a | Frequency | IR intensity a | |
C≡C stretch | Ag | 1645.2 | 0.00 | 1529.4 | 0.32 |
C–H stretch | Ag | 3036.3 | 0.00 | 3023.9 | 0.00 |
C–H stretch | B3g | 3089.8 | 0.00 | 3090.7 | 0.00 |
C–H stretch | B1u | 3021.3 | 0.64 | 3017.7 | 0.98 |
C–H stretch | B2u | 3117.5 | 1 | 3113.2 | 1 |
3.1.2. Realistic Cu1–ZSM-5 model
Configuration | Adsorbent | Electronic configuration |
---|---|---|
I | – | 4s ( 0.25) 3d ( 9.84) |
C2H2 | 4s ( 0.36) 3d ( 9.56) 4p ( 0.01) | |
C2H4 | 4s ( 0.37) 3d ( 9.57) 4p ( 0.01) | |
5-MR | – | 4s ( 0.42) 3d ( 9.73) |
C2H2 | 4s ( 0.36) 3d ( 9.57) 4p ( 0.01) | |
C2H4 | 4s ( 0.36) 3d ( 9.58) 4p ( 0.01) | |
6-MR | – | 4s ( 0.44) 3d ( 9.71) |
C2H2 | 4s ( 0.36) 3d ( 9.55) 4p ( 0.01) | |
C2H4 | 4s ( 0.37) 3d ( 9.57) 4p ( 0.01) |
Configuration a | Adsorbent | Binding mode | Cu–Cb | CCb | Estabilizationc | E(deform) d |
---|---|---|---|---|---|---|
I | C2H2 | η2 | 1.934, 1.935 | 1.239 | –34.4 | 2.6 |
5MR | C2H2 | η2 | 1.934, 1.960 | 1.238 | –14.6 | 20.4 |
6MR | C2H2 | η2 | 1.937, 1.938 | 1.240 | –14.4 | 22.5 |
I | C2H4 | η2 | 1.969, 1.974 | 1.386 | –32.4 | 2.3 |
5MR | C2H4 | η2 | 1.974, 1.979 | 1.385 | –14.3 | 17.8 |
6MR | C2H4 | η2 | 1.970, 1.972 | 1.386 | –14.7 | 20.3 |
3.2. ZSM-5 containing dicopper active center (Cu2–ZSM-5)
3.2.1. The small dicopper zeolite model
Adsorbent | Binding mode | Cu–Ca | CCa | SCu•••Cub | Estabilization’c |
---|---|---|---|---|---|
C2H2 | μ−η2: η2 | 1.932, 1.933 1.933, 1.934 | 1.297 | 2.888 | –69.6 |
C2H4 | μ−η2: η2 | 2.003, 2.003, 2.003, 2.003 | 1.449 | 3.735 | –58.6 |
Free C2H2 | C2H2 on Cu2-zeolite | ||||
---|---|---|---|---|---|
Symmetry | Frequency | IR intensitya | Frequency | IR intensitya | |
C≡C stretch | Σg+ | 2001.4 | 0.00 | 1557.1 | 1.44 |
C–H stretch | Σg+ | 3400.0 | 0.00 | 3170.0 | 0.90 |
C–H stretch | Σu+ | 3300.5 | 1 | 3127.8 | 1 |
Free C2H4 | C2H4 on Cu2-zeolite | ||||
---|---|---|---|---|---|
Symmetry | Frequency | IR intensity a | Frequency | IR intensity a | |
C≡C stretch | Ag | 1645.2 | 0.00 | 1469.4 | 0.00 |
C–H stretch | Ag | 3036.3 | 0.00 | 3004.9 | 0.00 |
C–H stretch | B3g | 3089.8 | 0.00 | 3085.4 | 0.00 |
C–H stretch | B1u | 3021.3 | 0.64 | 3001.8 | 17.10 |
C–H stretch | B2u | 3117.5 | 1 | 3100.5 | 1 |
3.2.2. Realistic Cu2–ZSM-5 model
Configuration a | Adsorbent | Binding mode | Cu–C b | CC b | SCu•••Cu c (ΔSCu•••Cud) | Estabilization e | E(deform) f |
---|---|---|---|---|---|---|---|
2NN | C2H2 | μ−η1: η1 | 1.896, 1,896 | 1.266 | 2.289 (–0.083) | –33.7 | 19.0 |
3NN | C2H2 | μ−η2: η2 | 1.915, 1.923, 1.987, 2.014 | 1.285 | 3.047 (0.486) | –35.8 | 24.7 |
4NN | C2H2 | μ−η2: η2 | 1.934, 1.939, 1.956, 1.990 | 1.286 | 3.236 (–3.134) | –19.0 | 45.7 |
5NN | C2H2 | μ−η2: η2 | 1.958, 1.960, 1.967, 1.974 | 1.284 | 3.315 (–3.127) | –19.1 | 47.2 |
2NN | C2H4 | μ−η1: η1 | 1.946, 1.943 | 1.421 | 2.253 (–0.119) | –30.1 | 18.0 |
3NN | C2H4 | μ−η1: η2 | 1.938, 2.034, 2.097 | 1.399 | 3.223 (0.662) | –16.4 | 25.5 |
4NN | C2H4 | μ−η2: η2 | 1.982, 1.987, 2.024, 2.038 | 1.442 | 3.730 (–2.640) | –13.6 | 41.9 |
5NN | C2H4 | μ−η2: η2 | 2.015, 2.028, 2.029, 2.034 | 1.441 | 3.787 (–2.655) | –16.6 | 43.1 |
4. Conclusions
Acknowledgements
References and Notes
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Yumura, T.; Hasegawa, S.; Itadani, A.; Kobayashi, H.; Kuroda, Y. The Variety of Carbon-Metal Bonds inside Cu-ZSM-5 Zeolites: A Density Functional Theory Study. Materials 2010, 3, 2516-2535. https://doi.org/10.3390/ma3042516
Yumura T, Hasegawa S, Itadani A, Kobayashi H, Kuroda Y. The Variety of Carbon-Metal Bonds inside Cu-ZSM-5 Zeolites: A Density Functional Theory Study. Materials. 2010; 3(4):2516-2535. https://doi.org/10.3390/ma3042516
Chicago/Turabian StyleYumura, Takashi, Saki Hasegawa, Atsushi Itadani, Hisayoshi Kobayashi, and Yasushige Kuroda. 2010. "The Variety of Carbon-Metal Bonds inside Cu-ZSM-5 Zeolites: A Density Functional Theory Study" Materials 3, no. 4: 2516-2535. https://doi.org/10.3390/ma3042516