Mechanistic insight into methanol electro-oxidation catalyzed by PtCu alloy

doi:10.1016/S1872-2067(21)63886-X

Abstract

Abstract:

In this work, we have performed density functional theory (DFT) calculations to investigate the methanol electro-oxidation reaction (MOR) catalyzed by the Pt, PtCu alloy and Cu. The complex reaction networks, including the intermediate dehydrogenation, water dissociation and anti-poison reaction steps, are systematically investigated to explore the mechanisms. At the standard condition of pH = 0 and zero potential, for Cu, most dehydrogenation steps along the favorable pathway are endergonic, making it less active in MOR. For the Pt and PtCu alloy, their dehydrogenation steps are mainly exergonic, but the formed CO intermediate binds too tightly on Pt, that can accumulate on active sites to poison the electro-catalyst. The CO can be consumed by the thermodynamic reaction with OH*, which comes from water dissociation. DFT calculation shows alloying the Pt with Cu could not only reduce the free energy barrier for binding between CO* and OH*, but also assist the water dissociation to produce more OH* for that anti-poison reaction. That makes the PtCu alloy more active than the pure Pt electrode in experiment. The results reveal the importance of anti-poison reaction and water dissociation in MOR, which could be applied to the rational design of more active alloy electro-catalysts in future.

Key words: Methanol electro-oxidation, Density functional theory, PtCu alloy, Electrode, Anti-poison catalyst

Wei Zhang, Guang-Jie Xia, Yang-Gang Wang. Mechanistic insight into methanol electro-oxidation catalyzed by PtCu alloy[J]. Chinese Journal of Catalysis, 2022, 43(1): 167-176.

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Intermediates	Pt(110)		Pt₃Cu		Cu(110)
Intermediates	ΔE_b	Site	ΔE_b	Site	ΔE_b	Site
CH₃OH	-0.95	top	-0.93	top	-0.71	bridge
CH₂OH	-3.11	top	-3.41	bridge	-2.08	bridge
CHOH	-4.11	bridge	-4.24	top	-2.37	bridge
COH	-5.50	bridge	-4.57	bridge	-3.30	bridge
CO	-2.50	bridge	-2.50	top	-1.12	bridge
HCO	-3.63	bridge	-3.69	bridge	-2.19	bridge
C(OH)₂	-3.50	top	-3.64	top	-2.00	bridge
CH₃O	-2.89	bridge	-3.02	bridge	-3.26	bridge
CH₂O	-1.53	bridge	-1.32	bridge	-0.68	hcp
H₂COOH	-2.68	bridge	-2.87	bridge	-3.14	bridge
HCOOH	-1.08	top	-1.02	top	-0.74	top
COOH	-3.70	bridge	-3.81	bridge	-2.77	bridge
H₂COO	-3.76	bridge	-3.56	hcp	-4.98	hcp
HCOO	-3.66	bridge	-3.68	bridge	-3.79	bridge
OH	-3.54	bridge	-3.7	bridge	-4.05	bridge

Intermediates	Pt(110)		Pt₃Cu		Cu(110)
Intermediates	ΔE_b	Site	ΔE_b	Site	ΔE_b	Site
CH₃OH	-0.95	top	-0.93	top	-0.71	bridge
CH₂OH	-3.11	top	-3.41	bridge	-2.08	bridge
CHOH	-4.11	bridge	-4.24	top	-2.37	bridge
COH	-5.50	bridge	-4.57	bridge	-3.30	bridge
CO	-2.50	bridge	-2.50	top	-1.12	bridge
HCO	-3.63	bridge	-3.69	bridge	-2.19	bridge
C(OH)₂	-3.50	top	-3.64	top	-2.00	bridge
CH₃O	-2.89	bridge	-3.02	bridge	-3.26	bridge
CH₂O	-1.53	bridge	-1.32	bridge	-0.68	hcp
H₂COOH	-2.68	bridge	-2.87	bridge	-3.14	bridge
HCOOH	-1.08	top	-1.02	top	-0.74	top
COOH	-3.70	bridge	-3.81	bridge	-2.77	bridge
H₂COO	-3.76	bridge	-3.56	hcp	-4.98	hcp
HCOO	-3.66	bridge	-3.68	bridge	-3.79	bridge
OH	-3.54	bridge	-3.7	bridge	-4.05	bridge

Elementary reaction step	Pt(110)	Pt₃Cu	Cu(110)
(R01) CH₃OH + * →CH₂OH* + H⁺ + e^-	-0.56	-0.78	0.51
(R02) CH₂OH* → CHOH* + H⁺ + e^-	-0.10	0.00	0.53
(R03) CHOH* → COH* + H⁺ + e^-	-0.01	1.00	0.43
(R04) COH* →CO* + H⁺ + e^-	-0.72	-1.68	-1.59
(R05) CO* + H₂O → CO* + OH* + H⁺+ e^-	0.43	0.28	-0.07
(R06) CO* + OH* → COOH* + *	0.36	0.47	0.47
(R07) COOH* → CO₂ + * + H⁺ + e^-	0.49	0.61	-0.39
(R08) CH₃OH + * → CH₃O* + H⁺+ e^-	0.05	-0.09	-0.33
(R09) CH₃O* → CH₂O* + H⁺+ e^-	-0.43	-0.13	0.75
(R10) CH₂OH* → CH₂O* + H⁺ + e^-	0.18	0.56	-0.09
(R11) CH₂O* + H₂O + * → CH₂O* + OH* + H⁺ + e^-	0.43	0.28	-0.07
(R12) CH₂O* → HCO* + H⁺ + e^-	-0.36	-0.61	0.20
(R13) CHOH* → HCO* + H⁺ + e^-	-0.09	-0.04	-0.41
(R14) HCO* → CO*+H⁺+e^-	-0.65	-0.64	-0.74
(R15) CH₂O* + OH* → H₂COOH* + *	0.59	0.40	-0.18
(R16) H₂COOH* → H₂COO* + H⁺ + e^-	0.37	0.75	-0.36
(R17) H₂COOH* → HCOOH* + H⁺ +e^-	-0.87	-0.65	-0.08
(R18) HCOOH* → COOH* + H⁺ + e^-	-0.37	-0.53	0.19
(R19) HCOOH* →HCOO*+H⁺+ e^-	-0.21	-0.28	-0.68
(R20) H₂COO* →HCOO*+H⁺+e^-	-1.45	-1.67	-0.41
(R21) HCOO* →CO₂ + * + H⁺ + e^-	0.33	0.35	0.49
(R22) COH* + H₂O + * → COH* + OH* + H⁺+ e^-	0.43	0.28	-0.07
(R23) COH* + OH* → C(OH)₂+	-0.53	-1.42	-0.70
(R24) C(OH)₂* → COOH* + H⁺ + e^-	0.17	0.20	-0.42
(R25) HCO* + OH* → HCOOH* + *	0.08	0.36	-0.46
(R26) HCO* + H₂O + * → HCO* + OH* + H⁺ + e^-	0.43	0.28	-0.07
(R27) H₂COH* + OH* → H₂COH+ O + H⁺ + e^-	0.55	0.93	1.24
(R28) H₂COH* + O* → H₂COOH* + *	0.21	0.03	-1.51
(R29) HCOH* + OH* → HCOH* + O* + H⁺ + e^-	0.55	0.93	1.24
(R30) HCOH* + O* → HCOOH+	-0.56	-0.61	-2.12
(R31) COH* + OH* → COH* + O* + H⁺ + e^-	0.55	0.93	1.24
(R32) COH* + O* → COOH+	-0.91	-2.14	-2.35
(R33) CO* + OH* → CO* + O* + H⁺ + e^-	0.55	0.93	1.24
(R34) CO* + O* → CO₂ + *	0.30	0.15	-1.15
(R35) HCO* + OH* → HCO* + O*+ H⁺ + e^-	0.55	0.93	1.24
(R36) HCO* + O* →HCOO* + *	-0.68	-0.84	-2.39
(R37) H₂CO* + OH* → H₂CO* + O*+H⁺+ e^-	0.55	0.93	1.24
(R38) H₂CO* + O* → H₂COO* + *	0.41	0.22	-1.78
(R39) H₂O+ → OH + H⁺ + e^-	0.43	0.28	-0.07
(R40) OH* → H⁺ + O* + e^-	0.55	0.93	1.24
(R41) H* → H⁺ + * + e^-	0.43	0.52	-0.03

Elementary reaction step	Pt(110)	Pt₃Cu	Cu(110)
(R01) CH₃OH + * →CH₂OH* + H⁺ + e^-	-0.56	-0.78	0.51
(R02) CH₂OH* → CHOH* + H⁺ + e^-	-0.10	0.00	0.53
(R03) CHOH* → COH* + H⁺ + e^-	-0.01	1.00	0.43
(R04) COH* →CO* + H⁺ + e^-	-0.72	-1.68	-1.59
(R05) CO* + H₂O → CO* + OH* + H⁺+ e^-	0.43	0.28	-0.07
(R06) CO* + OH* → COOH* + *	0.36	0.47	0.47
(R07) COOH* → CO₂ + * + H⁺ + e^-	0.49	0.61	-0.39
(R08) CH₃OH + * → CH₃O* + H⁺+ e^-	0.05	-0.09	-0.33
(R09) CH₃O* → CH₂O* + H⁺+ e^-	-0.43	-0.13	0.75
(R10) CH₂OH* → CH₂O* + H⁺ + e^-	0.18	0.56	-0.09
(R11) CH₂O* + H₂O + * → CH₂O* + OH* + H⁺ + e^-	0.43	0.28	-0.07
(R12) CH₂O* → HCO* + H⁺ + e^-	-0.36	-0.61	0.20
(R13) CHOH* → HCO* + H⁺ + e^-	-0.09	-0.04	-0.41
(R14) HCO* → CO*+H⁺+e^-	-0.65	-0.64	-0.74
(R15) CH₂O* + OH* → H₂COOH* + *	0.59	0.40	-0.18
(R16) H₂COOH* → H₂COO* + H⁺ + e^-	0.37	0.75	-0.36
(R17) H₂COOH* → HCOOH* + H⁺ +e^-	-0.87	-0.65	-0.08
(R18) HCOOH* → COOH* + H⁺ + e^-	-0.37	-0.53	0.19
(R19) HCOOH* →HCOO*+H⁺+ e^-	-0.21	-0.28	-0.68
(R20) H₂COO* →HCOO*+H⁺+e^-	-1.45	-1.67	-0.41
(R21) HCOO* →CO₂ + * + H⁺ + e^-	0.33	0.35	0.49
(R22) COH* + H₂O + * → COH* + OH* + H⁺+ e^-	0.43	0.28	-0.07
(R23) COH* + OH* → C(OH)₂+	-0.53	-1.42	-0.70
(R24) C(OH)₂* → COOH* + H⁺ + e^-	0.17	0.20	-0.42
(R25) HCO* + OH* → HCOOH* + *	0.08	0.36	-0.46
(R26) HCO* + H₂O + * → HCO* + OH* + H⁺ + e^-	0.43	0.28	-0.07
(R27) H₂COH* + OH* → H₂COH+ O + H⁺ + e^-	0.55	0.93	1.24
(R28) H₂COH* + O* → H₂COOH* + *	0.21	0.03	-1.51
(R29) HCOH* + OH* → HCOH* + O* + H⁺ + e^-	0.55	0.93	1.24
(R30) HCOH* + O* → HCOOH+	-0.56	-0.61	-2.12
(R31) COH* + OH* → COH* + O* + H⁺ + e^-	0.55	0.93	1.24
(R32) COH* + O* → COOH+	-0.91	-2.14	-2.35
(R33) CO* + OH* → CO* + O* + H⁺ + e^-	0.55	0.93	1.24
(R34) CO* + O* → CO₂ + *	0.30	0.15	-1.15
(R35) HCO* + OH* → HCO* + O*+ H⁺ + e^-	0.55	0.93	1.24
(R36) HCO* + O* →HCOO* + *	-0.68	-0.84	-2.39
(R37) H₂CO* + OH* → H₂CO* + O*+H⁺+ e^-	0.55	0.93	1.24
(R38) H₂CO* + O* → H₂COO* + *	0.41	0.22	-1.78
(R39) H₂O+ → OH + H⁺ + e^-	0.43	0.28	-0.07
(R40) OH* → H⁺ + O* + e^-	0.55	0.93	1.24
(R41) H* → H⁺ + * + e^-	0.43	0.52	-0.03