Catalysis Theoretical Study on Water Gas Shift Reaction of Au-based Binary Alloy Au12M(M=Cu,Pt,Ni)†

doi:10.7503/cjcu20180118

Abstract

Abstract:

The structural stability, thermodynamic stability and reactivity of Au₁₂M(M=Cu,Pt,Ni) alloy clusters doped with Cu, Pt and Ni were studied by density functional theory(DFT) calculations. The reaction mechanism of water gas shift reaction(WGSR) in gold-based binary alloy clusters was also discussed. The Au₁₂Ni alloy clusters were found to have the best stability and electron activity. The reaction mechanism of redox mechanism and carboxyl mechanism in gold-based binary alloy clusters was explored. The result shows that the WGSR on the Au₁₂Cu alloy is in accordance with the redox mechanism A, those on Au₁₂Pt and Au₁₂Ni alloy clusters are in accordance with the redox mechanism B. Comparing the optimal reaction path of the three clusters, Au₁₂Cu clusters show the best catalytic activity for WGSR.

Key words: Density functional theory, Au₁₂M cluster, Water gas shift reaction(WGSR), Redox mechanism, Carboxy mechanism

CLC Number:

O641

TrendMD:

FANG Lei, XIA Shengjie, XUE Jilong, MENG Yue, QIAN Mengdan, LUO Wei, ZHANG Xiaofeng, NI Zheming. Catalysis Theoretical Study on Water Gas Shift Reaction of Au-based Binary Alloy Au₁₂M(M=Cu,Pt,Ni)^†[J]. Chem. J. Chinese Universities, 2018, 39(8): 1721.

Figures/Tables 10

Fig.1 Geometric configuration of three Au12M(M=Cu,Pt,Ni) clusters

Fig.2 d Orbital partial density of state(PDOS) of three types of alloy clusters

Fig.3 Optimal adsorption configurations of each reaction species on three Au12M(M=Cu, Pt, Ni) clusters

Table 1 Adsorption site and adsorption energy of each reaction species on three Au12M(M=Cu,Pt,Ni) clusters

Species	Au₁₂Cu		Au₁₂Pt		Au₁₂Ni
Species	Adsorption site	E_ads/eV	Adsorption site	E_ads/eV	Adsorption site	E_ads/eV
O	top	-5.14	hol	-4.67	bri	-5.37
OH	bri	-3.12	hol	-3.35	bri	-3.63
H	hol	-2.23	bri	-2.97	top	-2.81
H₂O	top	-0.14	hol	-0.86	hol	-0.87
CO₂	hol	-0.17	bri	-0.50	top	-0.75
COOH	bri	-2.50	top	-2.49	hol	-2.73
CO	hol	-1.02	hol	-1.78	top	-2.40
H₂	hol	-0.34	hol	-0.88	hol	-0.96

Fig.4 Redox and carboxyl mechanisms for the WGSR over three Au12M(M=Cu,Pt,Ni) clusters

Table 2 Activation energy and reaction energy change of each reaction step on various Au12M(M=Cu, Pt, Ni) clusters#

Mechanism	Element reaction	Au₁₂Cu		Au₁₂Pt		Au₁₂Ni
Mechanism	Element reaction	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV
	1:H₂O+=H^+OH^*	0.52	0.39	1.16	0.44	0.82	0.10
Redox	2-a:OH^=O^+H^*	0.07	0.25	2.37	0.65	1.54	0.58
	2-b:OH^+OH^=H₂O^+O^	2.15	0.35	0.54	0.58	0.44	0.52
	3:CO^+O^=C $O 2 $ +	0.14	-0.64	0.13	-0.02	0.69	-0.80
Carboxyl	4:CO^+OH^=COOH^+	0.63	-0.11	0.81	0.24	0.85	0.32
	5-a:COOH^+=H^+C $O 2 $	1.72	-0.30	2.27	-0.19	1.18	-0.10
	5-b:COOH^+OH^=H₂O^+C $O 2 $	1.97	-0.20	0.43	-0.23	0.66	-0.05
	6:2H^= $H 2 $ +2^*	0.66	0.01	0.56	0.22	0.22	0.17

Table 2 Activation energy and reaction energy change of each reaction step on various Au12M(M=Cu, Pt, Ni) clusters#

Mechanism	Element reaction	Au₁₂Cu		Au₁₂Pt		Au₁₂Ni
Mechanism	Element reaction	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV
	1:H₂O+=H^+OH^*	0.52	0.39	1.16	0.44	0.82	0.10
Redox	2-a:OH^=O^+H^*	0.07	0.25	2.37	0.65	1.54	0.58
	2-b:OH^+OH^=H₂O^+O^	2.15	0.35	0.54	0.58	0.44	0.52
	3:CO^+O^=C $O 2 $ +	0.14	-0.64	0.13	-0.02	0.69	-0.80
Carboxyl	4:CO^+OH^=COOH^+	0.63	-0.11	0.81	0.24	0.85	0.32
	5-a:COOH^+=H^+C $O 2 $	1.72	-0.30	2.27	-0.19	1.18	-0.10
	5-b:COOH^+OH^=H₂O^+C $O 2 $	1.97	-0.20	0.43	-0.23	0.66	-0.05
	6:2H^= $H 2 $ +2^*	0.66	0.01	0.56	0.22	0.22	0.17

Fig.5 Variation of the reaction energy of WGSR on Au12Cu cluster(A) Redox mechanism; (B) carboxyl mechanism.

Fig.6 Variation of the reaction energy of WGSR on Au12Pt cluster(A) Redox mechanism; (B) carboxyl mechanism.

Fig.7 Variation of the reaction energy of WGSR on Au12Ni cluster(A) Redox mechanism; (B) carboxyl mechanism.

Fig.8 Comparison of the energy response of the optimal reaction paths for WGSR on three Au12M clusters

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Catalysis Theoretical Study on Water Gas Shift Reaction of Au-based Binary Alloy Au₁₂M(M=Cu,Pt,Ni)^†

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