Mn-corrolazine-based 2D-nanocatalytic material with single Mn atoms for catalytic oxidation of alkane to alcohol

doi:10.1016/S1872-2067(20)63707-X

Abstract

Abstract:

Heterogenization of organic-macrocyclic metal catalysts is one of the simplest and most efficient methods for effective separation of products and cyclic application of a catalyst. By using an environmentally friendly Mn-corrolazine catalyst as the building unit, which can directly oxidize organic substrates under oxygen atmosphere and mild conditions, we theoretically constructed a novel two-dimensional (2D) Mn-corrolazine nanocatalytic material with high catalytic activity. In this material, each Mn atom maintains its electronic configuration in the monomer and can directly activate O₂ as the single-atom catalyst (SAC) center to form a radical-like [Mn]-O-O under mild visible-light irradiation conditions. The newly generated [Mn]-O-O can efficiently and selectively oxidize C-H bonds to form alcohol species through H-abstraction and the rebound reaction. Moreover, the catalytic reaction is easily regulated by an external electric field along its intrinsic Mn-O-O reaction axis. The current study provides a theoretical foundation for further experimental studies and practical applications of the Mn-corrolazine-based SAC.

Key words: Single-atom catalyst, Heterogenization, Two-dimensional nanomaterials, First-principles calculations, C-H bond activation

Chun Zhu, Jin-Xia Liang, Yang Meng, Jian Lin, Zexing Cao. Mn-corrolazine-based 2D-nanocatalytic material with single Mn atoms for catalytic oxidation of alkane to alcohol[J]. Chinese Journal of Catalysis, 2021, 42(6): 1030-1039.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63707-X

https://www.cjcatal.com/EN/Y2021/V42/I6/1030

Figures/Tables 11

Scheme 1. Manganese corrolazine dimer (di-Mncor), tetramer (tetra-Mncor) and their extended two-dimensional nanocatalytic material (2D-Mncor) constructed by combining Mn-corrolazines and ethynes.

Fig. 1. Optimized geometries and relatively energies (kcal/mol) of di-Mncor in (a) singlet and (b) nonet states; tetra-Mncor in (c) singlet and (d) 17-et states (top view).

Table 1 Selected optimized bond lengths (?), Mulliken spin densities (ρspin) of Mn, magnetic moment (μB), and relative energies (ΔE, kcal/mol) of Mn(III)-corrolazine in di-Mncor in the singlet and nonet states, tetra-Mncor in the single and 17-et states, 2D-Mncor with ferromagnetism (FM) and antiferromagnetism (AFM).

Polymer (State)	d_Mn-N1 d_Mn-N2	d_Mn-N3 d_Mn-N4	d_c≡c	ΔE	ρ_spin/μ_B Mn
Di-Mn_cor (nonet)	1.864, 1.864 1.864, 1.864	1.860, 1.861 1.860, 1.861	1.218, 1.218	0.0	3.77, 3.77
Di-Mn_cor (singlet)	1.848, 1.848 1.848, 1.848	1.863, 1.863 1.863, 1.862	1.218, 1.218	98.65	—
Tetra-Mn_cor (17-et)	1.865, 1.878 1.866, 1.879 1.866, 1.880 1.866, 1.878	1.868, 1.867 1.868, 1.867 1.868, 1.867 1.868, 1.866	1.215, 1.222 1.215, 1.223 1.216, 1.224 1.216, 1.224	0.0	3.77, 3.77 3.77, 3.77
Tetra-Mn_cor (singlet)	1.847, 1.856 1.847, 1.856 1.847, 1.856 1.848, 1.856	1.865, 1.865 1.865, 1.865 1.865, 1.865 1.865, 1.865	1.216, 1.222 1.216, 1.222 1.217, 1.224 1.217, 1.224	194.38	—
2D-Mn_cor (FM)	1.903, 1.904 1.903, 1.904	1.885, 1.886 1.885, 1.886	1.230, 1.231	13.34	3.57, 3.57
2D-Mn_cor (AFM)	1.903, 1.904 1.903, 1.905	1.885, 1.886 1.885, 1.887	1.231, 1.231	0.0	3.65, -3.65

Fig. 2. Selected Mn-dominated molecular orbitals of the di-Mncor in the nonet state.

Table 2 The bond lengths of Mn-N (?), the relative energies (ΔG, kcal/mol) and Mulliken spin densities (ρspin), selected atoms’ magnetic moments (μB) of the complexes of O2 and Mn(III)-corrolazine in different states of di-O-Mncor, tetra-O-Mncor and 2D-Mncor.

Polymer (State)	d_Mn-N1 d_Mn-N2	d_Mn-N3 d_Mn-N4	d_O-O	ΔE	ρ_spin/μ_B
Polymer (State)	d_Mn-N1 d_Mn-N2	d_Mn-N3 d_Mn-N4	d_O-O	ΔE	^aO	^bO	Mn
Di-O-Mn_cor (13-et)	1.867, 1.868 1.867, 1.868	1.865, 1.864 1.864, 1.864	1.214 1.214	0.0	1.03 1.03	0.98 0.98	3.77 3.77
Di-O-Mn_cor (quintet)	1.874, 1.874 1.874, 1.873	1.871, 1.871 1.871, 1.871	1.216 1.216	2.98	-1.03 -1.03	-0.92 -0.92	3.74 3.74
Di-O-Mn_cor (singlet)	1.871, 1.877 1.873, 1.876	1.899, 1.894 1.896, 1.894	1.256 1.256	84.14	—	—	—
Tetra-O-Mn_cor (singlet)	1.858, 1.897 1.865, 1.894 1.858, 1.897 1.865, 1.894	1.886, 1.894 1.893, 1.898 1.886, 1.894 1.893, 1.898	1.254 1.255 1.255 1.256	—	—	—	—
2D-O-Mn_cor (spin-polarized)	1.921, 1.923 1.920, 1.921	1.903, 1.902 1.903, 1.904	1.262 1.262	0.0	-0.73 0.73	-0.58 0.57	3.58 -3.58
2D-O-Mn_cor (spin-unpolarized)	1.925, 1.929 1.927, 1.928	1.917, 1.918 1.917, 1.918	1.267 1.267	74.53	—	—	—

Fig. 3. Optimized geometries of di-O-Mncor complexes consisting of O2 and di-Mncor in (a) singlet, (b) quintet, and (c) 13-et states. (d) Tetra-O-Mncor in the singlet state consisting of O2 and tetra-Mncor with specific bond lengths (?).

Fig. 4. The optimized structures of quintet-, triplet- and singlet-state complexes of Mn(III)-corrolazine and 3[O2] and the energy difference between corresponding two complexes with different spin multiplicities.

Fig. 5. (a) Optimized geometry and (b) the electronic band structure of 2D-Mncor nanomaterial

Fig. 6. The predicted reaction pathway for the generation of cyclohexanol and the Mn(V)-oxo unit catalyzed by the 2D-O-Mncor nanomaterial in the spin-unpolarized state (relative energies and selected bond lengths are in kcal/mol and ?, respectively).

Fig. 7. Proposed reaction pathway for CH4 activation on the 2D-O-Mncor nanomaterial in the spin-unpolarized state (relative energies and selected bond lengths are in kcal/mol and ?, respectively).

Fig. 8. Predicted barriers for the conversion of CH4 to CH3OH under various external electric fields.

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