Understanding the Reactivity of Single Atom Alloys towards the Alkyl C–H Bond Activation: A theoretical Study

Congcong Qiao,
Gang Fu^,

State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China

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Corresponding author: E-mail: gfu@xmu.edu.cn

摘要

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Abstract: Single atom alloys (SAAs), composed of active metal dopants atomically dispersed on the Cu, Ag, or Au host metals, have recently become a ‘rising star’ in single atom catalysis research. SAAs usually display unique catalytic behavior, mainly due to the anomalous electronic structure of isolated active sites, distinguishing from that of the parent metals. As the consequence, there is lack of robust yet reliable descriptor of catalytic properties of SAAs. In this work, we present a systematically theoretical study on the first C–H bond activation of methane, propane and ethylbenzene over 15 SAAs comprising of Rh, Ir, Ni, Pd, and Pt doping Cu(111), Ag(111), and Au(111) surfaces. Our DFT calculations demonstrate that not only the d-band centers but also the H atom adsorption energies could not correlate well with the activation barriers of alkyl C–H bond, while enhanced performance is achieved when using the reaction energy as a descriptor. We find that there existed orbital interaction similarity between C atom adsorption on top site and the transition states of C–H activation because both of them involve not only σ donation with d_z² orbital but also the π back-donation from d_xy/d_yz orbital(s). As a consequence, the C adsorption energies and C–H bond activation energies are very strongly correlated (R²>0.9), not only for methane but also for propane and ethylbenzene.
- Single-atom alloy /
- C–H bond activation /
- d-band center /
- Thermochemical descriptor /
- Linear scaling

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Figure 1. The top view (a) and side view (b) of the SAA model.

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Figure 2. Geometry of the initial state, transition state, and final state for the first C–H activation of methane.

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Figure 3. The correlation between the activation barriers (ΔE_a) and the d-band center (ε_d) (a) , ΔE_a and reaction energies (ΔE_rxn) (b) ; ΔE _a and H atom adsorption energies (E_H) (c) , ΔE_a and C atom adsorption energies (E_C) (d) . The solid squares represent the SAAs while the hollow squares represent the pure metals.

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Figure 4. Comparison of the orbital interaction between C-H bond activation and H or C atom adsorption on SAAs/metals.

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Figure 5. The correlation of the ΔE_a of different C–H bonds with E_C.

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Table I. The electronic structures and reactivity of different SAAs and their parent metals (energy in eV, bond length in Å).

Surfaces	ε_d	ΔE_ads	CH₃–H activation				ΔE_rxn
Surfaces	ε_d	ΔE_ads	ΔE_a	d_C–H	d_M–C	d_M–H	ΔE_rxn
Rh(111)	−1.57	−0.01	0.75	1.552	2.213	1.645	0.29
Rh₁Cu(111)	−0.75	−0.02	0.70	1.641	2.204	1.618	0.43
Rh₁Ag(111)	−0.43	−0.05	0.56	1.614	2.218	1.604	0.37
Rh₁Au(111)	−0.55	−0.10	0.66	1.667	2.171	1.595	0.51
Ir(111)	−2.00	−0.01	0.77	1.488	2.266	1.658	0.32
Ir₁Cu(111)	−0.91	0.00	0.50	1.497	2.268	1.639	0.11
Ir₁Ag(111)	−0.52	−0.05	0.33	1.432	2.266	1.636	−0.03
Ir₁Au(111)	−0.70	−0.08	0.31	1.477	2.242	1.616	0.04
Ni(111)	−1.16	−0.02	0.92	1.594	2.064	1.558	0.35
Ni₁Cu(111)	−0.62	0.00	0.82	1.647	2.064	1.522	0.38
Ni₁Ag(111)	−0.35	−0.01	0.85	1.707	2.021	1.514	0.69
Ni₁Au(111)	−0.44	−0.02	0.88	1.791	2.001	1.536	0.78
Pd(111)	−1.37	−0.01	0.84	1.586	2.173	1.657	0.35
Pd₁Cu(111)	−1.67	0.00	1.21	1.720	2.207	1.637	0.79
Pd₁Ag(111)	−1.26	−0.03	1.26	1.732	2.185	1.619	1.04
Pd₁Au(111)	−1.19	−0.04	1.17	1.750	2.172	1.621	0.95
Pt(111)	−1.75	−0.01	0.70	1.489	2.221	1.652	−0.07
Pt₁Cu(111)	−1.71	0.00	1.05	1.592	2.250	1.632	0.55
Pt₁Ag(111)	−1.25	0.00	0.99	1.550	2.237	1.622	0.60
Pt₁Au(111)	−1.30	0.00	0.73	1.579	2.208	1.615	0.35

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