Theoretical Study of Dry Reforming of Methane Catalyzed by Bimetallic Alloy Cluster M12Ni(M=Pt, Sn, Cu) †

doi:10.7503/cjcu20190267

Abstract

Abstract:

The electronic activity and structural stability of three bimetallic alloy clusters of M₁₂Ni(M=Pt, Sn, Cu) were studied by density functional theory(DFT). The change of the methane dry reforming reaction(DRM) on three clusters M₁₂Ni(M=Pt, Sn, Cu) was also discussed. It is found that the methane dehydrogenation and carbon dioxide activation process exhibit the lowest activation energy barrier to be overcome on the surface of Pt₁₂Ni cluster, so these two processes are the most potential to carry out over Pt₁₂Ni cluster. The formation of carbon on the Sn₁₂Ni cluster requires higher activation energy, indicating that the Sn₁₂Ni cluster can effectively inhibit the formation of carbon. To some extent, it overcomes the catalyst deactivation caused by carbon deposition. And the Sn₁₂Ni cluster exhibits the best catalytic activity during the oxidation of C ^* and CH ^*. The Cu₁₂Ni cluster shows excellent catalytic activity only during the dehydrogenation of methane.

Key words: Density functional theory, Alloy cluster, Dry reforming of methane(DRM), Energy barrier

CLC Number:

O641
O643

TrendMD:

CHEN Tao,FANG Lei,LUO Wei,MENG Yue,XUE Jilong,XIA Shengjie,NI Zheming. Theoretical Study of Dry Reforming of Methane Catalyzed by Bimetallic Alloy Cluster M₁₂Ni(M=Pt, Sn, Cu) ^†[J]. Chem. J. Chinese Universities, 2019, 40(10): 2135.

Figures/Tables 13

Fig.1 Geometric configuration of three M12Ni(M=Pt, Sn, Cu) clusters

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

Species	Pt₁₂Ni		Sn₁₂Ni		Cu₁₂Ni
Species	Optimum adsorption site	E_ads/eV	Optimum adsorption site	E_ads/eV	Optimum adsorption site	E_ads/eV
C $H 4 *$	TOP	-0.282	HOL	-0.201	TOP	-0.267
C $H 3 *$	TOP	-2.626	HOL	-2.008	TOP	-2.393
C $H 2 *$	HOL	-4.713	TOP	-2.973	TOP	-4.276
CH^*	HOL	-6.744	BRI	-4.530	TOP	-6.033
C^*	HOL	-7.102	HOL	-3.655	TOP	-5.879
C $O 2 *$	HOL	-0.596	HOL	-0.186	BRI	-0.524
CO^*	TOP	-2.534	HOL	-0.217	TOP	-1.656
H^*	TOP	-2.933	TOP	-2.123	HOL	-2.858
$H 2 *$	TOP	-1.192	BRI	-0.134	BRI	-0.403
O^*	HOL	-4.501	BRI	-4.567	BRI	-5.786
OH^*	BRI	-2.976	BRI	-2.850	HOL	-3.844
H₂O^*	HOL	-0.589	HOL	-0.263	TOP	-0.632
CHO^*	BRI	-3.968	BRI	-1.464	BRI	-3.125
COH^*	HOL	-4.009	TOP	-3.024	TOP	-3.913
COOH^*	TOP	-3.114	HOL	-1.824	BRI	-2.799
CHOH^*	HOL	-3.719	BRI	-1.823	BRI	-3.157

Species	Pt₁₂Ni		Sn₁₂Ni		Cu₁₂Ni
Species	Optimum adsorption site	E_ads/eV	Optimum adsorption site	E_ads/eV	Optimum adsorption site	E_ads/eV
C $H 4 *$	TOP	-0.282	HOL	-0.201	TOP	-0.267
C $H 3 *$	TOP	-2.626	HOL	-2.008	TOP	-2.393
C $H 2 *$	HOL	-4.713	TOP	-2.973	TOP	-4.276
CH^*	HOL	-6.744	BRI	-4.530	TOP	-6.033
C^*	HOL	-7.102	HOL	-3.655	TOP	-5.879
C $O 2 *$	HOL	-0.596	HOL	-0.186	BRI	-0.524
CO^*	TOP	-2.534	HOL	-0.217	TOP	-1.656
H^*	TOP	-2.933	TOP	-2.123	HOL	-2.858
$H 2 *$	TOP	-1.192	BRI	-0.134	BRI	-0.403
O^*	HOL	-4.501	BRI	-4.567	BRI	-5.786
OH^*	BRI	-2.976	BRI	-2.850	HOL	-3.844
H₂O^*	HOL	-0.589	HOL	-0.263	TOP	-0.632
CHO^*	BRI	-3.968	BRI	-1.464	BRI	-3.125
COH^*	HOL	-4.009	TOP	-3.024	TOP	-3.913
COOH^*	TOP	-3.114	HOL	-1.824	BRI	-2.799
CHOH^*	HOL	-3.719	BRI	-1.823	BRI	-3.157

Fig.3 Elementary reaction of dry reforming of methane

Elementary reaction	Pt₁₂Ni		Sn₁₂Ni		Cu₁₂Ni
Elementary reaction	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV
C $H 4 $ =C $H 3 $ +H^*	0.295	-0.252	2.981	1.687	1.142	0.009
C $H 3 $ =C $H 2 $ +H^*	0.577	-0.003	3.809	2.348	1.548	0.322
C $H 2 $ =CH^+H^*	0.187	-0.160	0.802	0.016	0.031	-0.004
CH^=C^+H^*	0.238	-0.717	2.809	2.306	0.601	0.005

Elementary reaction	Pt₁₂Ni		Sn₁₂Ni		Cu₁₂Ni
Elementary reaction	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV
C $H 4 $ =C $H 3 $ +H^*	0.295	-0.252	2.981	1.687	1.142	0.009
C $H 3 $ =C $H 2 $ +H^*	0.577	-0.003	3.809	2.348	1.548	0.322
C $H 2 $ =CH^+H^*	0.187	-0.160	0.802	0.016	0.031	-0.004
CH^=C^+H^*	0.238	-0.717	2.809	2.306	0.601	0.005

Fig.4 Energy change of methane dehydrogenation process on three clusters

Elementary reaction	Pt₁₂Ni		Sn₁₂Ni		Cu₁₂Ni
Elementary reaction	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV
C $O 2 $ =CO^+O^*	0.710	0.354	3.337	3.049	1.284	-0.145
C $O 2 $ +H^=COOH^*	0.499	0.035	3.316	0.204	4.607	1.228
COOH^=CO^+OH^*	1.180	-0.235	1.494	0.657	0.589	-0.787

Elementary reaction	Pt₁₂Ni		Sn₁₂Ni		Cu₁₂Ni
Elementary reaction	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV
C $O 2 $ =CO^+O^*	0.710	0.354	3.337	3.049	1.284	-0.145
C $O 2 $ +H^=COOH^*	0.499	0.035	3.316	0.204	4.607	1.228
COOH^=CO^+OH^*	1.180	-0.235	1.494	0.657	0.589	-0.787

Fig.5 Energy change of carbon dioxide activation process on three clusters

Elementary reaction	Pt₁₂Ni		Sn₁₂Ni		Cu₁₂Ni
Elementary reaction	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV
C^+O^=CO^*	0.150	-0.481	0.046	-0.006	0.235	-0.020
C^+OH^=COH^*	1.413	0.822	0.140	0.017	0.642	-0.003
COH^=CO^+H^*	1.372	-2.013	1.736	-1.101	1.872	-1.295
CH^+O^=CHO^*	0.222	0.036	0.049	-0.235	1.983	-0.195
CHO^=CO^+H^*	0.092	-1.041	1.576	0.434	0.396	-0.679
CH^+OH^=CHOH^*	3.536	1.460	0.964	0.239	1.541	0.850
CHOH^=CHO^+H^*	2.541	-0.889	2.378	-1.060	0.012	-0.850
CHOH^=COH^+H^*	3.081	0.340	2.394	1.663	0.920	-0.003

Fig.6 Energy change of C* oxidation process on three clusters (A) C*+O*=CO*; (B) C*+OH*=COH*.

Fig.7 Energy change of CH* oxidation process on three clusters

Elementary reaction	Pt₁₂Ni		Sn₁₂Ni		Cu₁₂Ni
Elementary reaction	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV
H^+H^= $H 2 *$	0.389	0.002	0.668	-1.128	1.296	0.619
H^+OH^=H₂O	0.617	-0.378	0.343	-1.132	1.954	0.343

Elementary reaction	Pt₁₂Ni		Sn₁₂Ni		Cu₁₂Ni
Elementary reaction	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV	E_a/eV	ΔE/eV
H^+H^= $H 2 *$	0.389	0.002	0.668	-1.128	1.296	0.619
H^+OH^=H₂O	0.617	-0.378	0.343	-1.132	1.954	0.343

Fig.8 Energy changes of generate H2(A) and H2O(B) process on three clusters

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Theoretical Study of Dry Reforming of Methane Catalyzed by Bimetallic Alloy Cluster M₁₂Ni(M=Pt, Sn, Cu) ^†

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