Substituent Effects of the Nitrogen Heterocycle on Indole and Quinoline HDN Performance: A Combination of Experiments and Theoretical Study
Abstract
:1. Introduction
2. Results and Discussion
2.1. HDN Behaviors of Indole and Quinoline on the Ni-Mo-S/γ-Al2O3 Catalyst
2.1.1. Experimental Phenomenon
2.1.2. Theoretical Explanation
2.2. Substituent Effects of the Heterocycle on the HDN Behavior
2.2.1. Substituent Effects on the Indole HDN
2.2.2. Theoretical Explanation
2.2.3. Substituent Effects on the Quinoline Self-HDN Behavior on Ni-Mo-S/γ-Al2O3
2.2.4. Theoretical Explanation
2.2.5. Substituent Effects on Quinoline HDN Competitive Ability
2.2.6. Theoretical Explanation
3. Materials and Methods
3.1. Experimental
3.1.1. Preparation of the NiMo/γ-Al2O3 Catalysts
3.1.2. HDN Evaluation and Analysis
3.2. Theoretical Calculation
3.2.1. Modeling
3.2.2. Computational Methods
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Indole | Quinoline | ||||
---|---|---|---|---|---|
Product | Formula | Structural | Product | Formula | Structural |
Ethyl-cyclohexane (ECH) | C8H16 | Propyl-cyclohexane (PCH) | C9H18 | ||
Ethyl-benzene (EB) | C8H10 | Propyl-benzene (PB) | C9H12 | ||
Ethyl-cyclohexene (ECHE) | C8H14 | Propyl-cyclohexene (PCHE) | C9H16 | ||
o-Ethylaniline (OEA) | C8NH15 | Decahydroquinoline (DHQ) | C9NH17 | ||
Indoline (DHI) | C8NH9 | o-Propylaniline (OPA) | C9NH13 | ||
Indole (IND) | C8NH7 | 5,6,7,8-Tetrahydroquinoline (THQ-5) | C9NH11 | ||
Quinoline (QL) | C9NH7 | ||||
1,2,3,4-Tetrahydroquinoline (THQ-1) | C9NH11 |
Reactant | Relative Concentration, m/m% | ||||||||
---|---|---|---|---|---|---|---|---|---|
Indole | LHSV/h−1 | IND | DHI | OEA | ECHE | EB | ECH | ||
20.0 | 60.92 | 20.96 | 7.42 | 2.67 | 2.54 | 5.49 | |||
10.0 | 36.52 | 12.14 | 18.24 | 4.84 | 2.86 | 25.16 | |||
5.0 | 18.19 | 7.48 | 18.94 | 3.92 | 1.57 | 49.95 | |||
2.5 | 7.03 | 1.92 | 3.81 | 1.02 | 1.34 | 85.39 | |||
Quinoline | LHSV/h−1 | THQ-1 | QL | THQ-5 | OPA | DHQ | PCHE | PB | PCH |
20.0 | 79.77 | 1.92 | 8.20 | 0.22 | 6.16 | 1.10 | 0.29 | 2.34 | |
10.0 | 64.89 | 1.49 | 11.83 | 1.10 | 10.99 | 2.45 | 0.52 | 7.25 | |
5.0 | 36.24 | 0.74 | 15.86 | 1.65 | 15.64 | 3.67 | 2.12 | 24.22 | |
2.5 | 21.46 | 0.39 | 15.30 | 1.82 | 11.70 | 2.77 | 1.82 | 43.74 |
Position | Step | Indole Adsorption | TS-1 | Hydrogen Activation | TS-2 |
Ni-S-edge | Morphology | - | - | ||
ΔE/kJ·mol−1 | −124.18 | +128.27 | |||
Ni-Mo-edge | Morphology | ||||
ΔE/kJ·mol−1 | −121.63 | +145.09 | −108.42 | +129.65 | |
Position | Step | Monohydrogen- Indole | TS-3 | DHI | Desorption |
Ni-S-edge | Morphology | ||||
ΔE/kJ·mol−1 | −96.20 | +108.75 | −202.39 | +163.85 | |
Ni-Mo-edge | Morphology | ||||
ΔE/kJ·mol−1 | −133.33 | +101.24 | −220.00 | ||
Position | Step | Quinoline Adsorption | TS-1 | Hydrogen Activation | TS-2 | Monohydrogen-Quinoline | TS-3 | Dihydrogen -Quinoline |
---|---|---|---|---|---|---|---|---|
Ni-S -edge | Morphology | - | - | |||||
ΔE/kJ·mol−1 | −169.22 | +140.22 | −109.88 | +114.82 | −87.56 | |||
Ni-Mo -edge | Morphology | |||||||
ΔE/kJ·mol−1 | −146.34 | +90.67 | −85.79 | +115.98 | −137.52 | +64.83 | −82.22 | |
Step | TS-4 | Hydrogen Activation | TS-5 | Tri-hydrogen -quinoline | TS-6 | THQ-1 | Desorption | |
Ni-S -edge | Morphology | |||||||
ΔE/kJ·mol−1 | +127.12 | −186.74 | +102.68 | −110.58 | +85.99 | −143.26 | +163.85 | |
Ni-Mo -edge | Morphology | |||||||
ΔE/kJ·mol−1 | +144.33 | −100.79 | +95.55 | −81.09 | +76.77 | −198.53 | ||
Reaction Pathway | SN2 | E2 Step1 | E2 Step2 |
---|---|---|---|
Reaction equation | |||
Pre-hydrogenolysis | |||
Transition state | |||
Post-hydrogenolysis | |||
Activation energy/kJ·mol−1 | +269.39 | +136.93 | +132.47 |
Reaction energy/kJ·mol−1 | −57.87 | +56.75 | +59.02 |
Nitrogen Compounds | DHI | C–N Bond Cleavage | |
---|---|---|---|
Bonding Energy Difference/kJ·mol−1 | 281.84 | ||
Molecular orbitals participating in adsorption | |||
MO Eigenvalue/eV | −4.56 | −4.51 | −5.76 |
Adsorption morphology | |||
Adsorption energy/kJ·mol−1 | −156.88 | −258.59 | |
Reaction | ||
---|---|---|
Initial state | ||
Transition state | ||
Final state | ||
Activation energy/kJ·mol−1 | +142.37 | +208.81 |
Reaction energy/kJ·mol−1 | +75.97 | +95.02 |
Nitrogen Compounds | ||||
---|---|---|---|---|
Molecular orbitals participate in adsorption | ||||
MO Eigenvalue/eV | −4.84 | −5.72 | −4.91 | −5.90 |
Reaction | ||
---|---|---|
Initial state | ||
Transition state | ||
Final state | ||
Activation energy/kJ·mol−1 | +130.25 | +172.85 |
Reaction energy/kJ·mol−1 | +81.54 | +80.44 |
Reactant | Relative Concentration of HDN Products, m/m% | ||||||
---|---|---|---|---|---|---|---|
2-Methyl -indole | LHSV/h−1 | ||||||
2-M-IND | DH-2-M-IND | OPA | PCHE | PCH | i-PCH | ||
20.0 | 68.96 | 10.84 | 7.42 | 1.91 | 14.17 | 0.59 | |
10.0 | 46.29 | 6.56 | 8.24 | 1.52 | 33.13 | 1.19 | |
5.0 | 27.40 | 2.09 | 4.33 | 2.09 | 52.95 | 2.81 | |
2.5 | 13.73 | 1.73 | 2.42 | 1.95 | 75.86 | 3.71 | |
3-Methyl -indole | LHSV/h−1 | 3-M-IND | DH-3-M-IND | i-OPEA | i-OPA | i-PCHE | i-PCH |
20.0 | 78.84 | 4.93 | 1.21 | 3.53 | 2.19 | 9.30 | |
10.0 | 59.14 | 4.82 | 1.24 | 5.76 | 2.17 | 26.87 | |
5.0 | 40.56 | 1.85 | 1.57 | 5.81 | 2.31 | 47.90 | |
2.5 | 22.11 | 0.66 | 1.58 | 3.73 | 1.43 | 70.49 |
Reaction | |||
---|---|---|---|
Reactant | Indole | 2-Methyl-Indole | 3-Methyl-Indole |
Adsorption morphology | |||
Adsorption energy/kJ·mol−1 | −124.18 | −131.32 | −117.66 |
Transition state | |||
Activation energy/kJ·mol−1 | +128.27 | +151.35 | +156.48 |
Final state | |||
Reaction energy/kJ·mol−1 | +32.29 | +60.74 | +72.57 |
Relative Concentration, m/m% | ||||||||
---|---|---|---|---|---|---|---|---|
2-Methyl -quinoline LHSV/h−1 | 2-M- THQ-1 | OBA | 2-M-QL | 2-M- THQ-5 | 2-M-DHQ | 1-BCHE | 2-BCHE | BCH |
20.0 | 72.57 | 2.04 | 4.17 | 9.03 | 7.21 | 1.16 | 0.82 | 3.06 |
10.0 | 57.05 | 4.33 | 4.16 | 12.49 | 11.30 | 2.17 | 1.63 | 6.87 |
5.0 | 35.94 | 5.47 | 3.27 | 14.20 | 12.03 | 1.71 | 0.13 | 27.25 |
2.5 | 22.49 | 1.16 | 2.20 | 14.75 | 11.24 | 1.22 | 1.29 | 45.65 |
3-Methyl -quinoline LHSV/h−1 | 3-M- THQ-1 | 3-M-QL | 3-M- THQ-5 | i-OBA | 3-M-DHQ | 1-i-BCHE | 2-i-BCHE | i-BCH |
20.0 | 72.73 | 4.88 | 11.27 | 0.81 | 8.16 | 0.58 | 0.11 | 1.46 |
10.0 | 59.10 | 3.95 | 14.49 | 1.73 | 13.55 | 1.24 | 0.23 | 5.71 |
5.0 | 36.69 | 3.84 | 17.13 | 2.36 | 19.91 | 2.29 | 0.40 | 15.37 |
2.5 | 24.88 | 2.50 | 13.14 | 2.39 | 25.22 | 1.26 | 1.88 | 28.73 |
Reaction | |||
---|---|---|---|
Reactant | DHQ | 2-M-DHQ | 3-M-DHQ |
Initial state | |||
Transition state | |||
Activation energy/kJ·mol−1 | +172.85 | +174.59 | +201.08 |
Final state | |||
Reaction energy/kJ·mol−1 | +80.44 | +86.71 | +82.93 |
Relative Concentration, m/m% | |||||||||
---|---|---|---|---|---|---|---|---|---|
2-M-QL | LHSV/h−1 | 2-M- THQ-1 | OBA | 2-M-Q | 2-M- THQ-5 | 2-M-DHQ | 1-BCHE | 2-BCHE | BCH |
20.0 | 57.24 | 0.62 | 27.13 | 9.51 | 4.73 | 0.11 | 0.24 | 0.42 | |
10.0 | 48.86 | 2.61 | 25.62 | 12.59 | 9.31 | 0.14 | 0.17 | 0.70 | |
5.0 | 44.55 | 2.38 | 13.2 | 15.13 | 17.43 | 0.27 | 0.25 | 6.79 | |
2.5 | 26.85 | 4.96 | 7.27 | 12.26 | 25.5 | 1.14 | 0.41 | 21.61 | |
QL | LHSV/h−1 | THQ-1 | Q | THQ-5 | DHQ | PB | PCHE | PCH | |
20.0 | 74.63 | 7.07 | 9.64 | 5.52 | 1.19 | 0.29 | 1.66 | ||
10.0 | 61.79 | 6.12 | 13.7 | 12.2 | 1.83 | 0.45 | 3.91 | ||
5.0 | 47.31 | 3.3 | 19.24 | 11.27 | 3.41 | 1.33 | 14.14 | ||
2.5 | 24.28 | 2.32 | 24.76 | 7.11 | 2.15 | 1.13 | 38.25 |
Relative Concentration, m/m% | |||||||||
---|---|---|---|---|---|---|---|---|---|
3-M-QL | LHSV/h−1 | 3-M- THQ-1 | 3-M -QL | 3-M- THQ-5 | i- OBA | 3-M -DHQ | 1-i- BCHE | 2-i- BCHE | i- BCH |
20.0 | 60.22 | 13.54 | 12.19 | 5.54 | 4.78 | 0.21 | 0.09 | 3.43 | |
10.0 | 56.34 | 11.67 | 12.01 | 3.82 | 11.07 | 0.25 | 0.1 | 4.74 | |
5.0 | 44.59 | 8.22 | 16.17 | 3.2 | 12.95 | 1.32 | 0.76 | 12.79 | |
2.5 | 29.24 | 4.42 | 16.49 | 3.02 | 18.34 | 2.00 | 1.12 | 25.37 | |
QL | LHSV/h−1 | THQ-1 | Q | THQ-5 | DHQ | PB | PCHE | PCH | |
20.0 | 76.13 | 12.51 | 1.36 | 7.59 | 0 | 0.53 | 1.88 | ||
10.0 | 71.51 | 9.06 | 1.49 | 11.08 | 0 | 1.50 | 5.36 | ||
5.0 | 54.48 | 5.13 | 6.97 | 13.2 | 1.29 | 3.11 | 15.82 | ||
2.5 | 35.46 | 2.7 | 10.49 | 8.79 | 1.54 | 1.29 | 39.73 |
Nitrogen Compound | Molecular Orbital of Lone Pair Electrons | Adsorption Morphology | N-Ni Bond Length/Å | Adsorption Energy/kJ·mol−1 |
---|---|---|---|---|
Quinoline | 2.11 | −146.34 | ||
2-Mythel- quinoline | 2.19 | −118.87 | ||
3-Mythel- quinoline | 2.10 | −150.01 | ||
Item | Parameter | ||
---|---|---|---|
Function | General Gradient Approximation Perdew–Burke–Ernzerhof Function (GGA-RPBE) [37,51,52] | ||
Basis set | Double numerical plus polarization basis (DNP) [41,53] | ||
Electron spin | Open shell/unrestricted | ||
Symmetry | Asymmetry | ||
Self-consistent field density convergence (SCF) | 2 × 10−5 | ||
Thermal smearing | 1 × 10−3 Hartree (Ha) | ||
Orbital cut-off | 4.90 angstroms (Å) | ||
Core treatment | Effective core potentials (ECP) | ||
Dispersion correction | Grimme 06 [54] | ||
Exchange-correlation-dependent factor, s6 | 1.0 [55] | ||
Damping coefficient, d | 20.0 [56] | ||
Grimme 6.0 Atomic dispersion [57] | Element | Interaction distance, R0 | Dispersion coefficient C6 |
H | 1.001 | 1.451 | |
C | 1.452 | 18.134 | |
N | 1.397 | 12.748 | |
S | 1.683 | 57.729 | |
Ni | 1.562 | 111.943 | |
Mo | 1.639 | 255.686 |
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Jiang, S.; Ding, S.; Zhou, Y.; Yuan, S.; Geng, X.; Cao, Z. Substituent Effects of the Nitrogen Heterocycle on Indole and Quinoline HDN Performance: A Combination of Experiments and Theoretical Study. Int. J. Mol. Sci. 2023, 24, 3044. https://doi.org/10.3390/ijms24033044
Jiang S, Ding S, Zhou Y, Yuan S, Geng X, Cao Z. Substituent Effects of the Nitrogen Heterocycle on Indole and Quinoline HDN Performance: A Combination of Experiments and Theoretical Study. International Journal of Molecular Sciences. 2023; 24(3):3044. https://doi.org/10.3390/ijms24033044
Chicago/Turabian StyleJiang, Shujiao, Sijia Ding, Yasong Zhou, Shenghua Yuan, Xinguo Geng, and Zhengkai Cao. 2023. "Substituent Effects of the Nitrogen Heterocycle on Indole and Quinoline HDN Performance: A Combination of Experiments and Theoretical Study" International Journal of Molecular Sciences 24, no. 3: 3044. https://doi.org/10.3390/ijms24033044