双金属合金团簇M12Ni(M=Pt, Sn, Cu)催化甲烷干法重整反应的理论研究

doi:10.7503/cjcu20190267

摘要/Abstract

摘要：

利用密度泛函理论(DFT)研究了M₁₂Ni(M=Pt, Sn, Cu) 3种双金属合金团簇的电子活性和结构稳定性, 并探讨了甲烷干法重整反应(DRM)在M₁₂Ni双金属团簇表面的反应能量变化情况. 经比较发现甲烷脱氢和二氧化碳活化过程在Pt₁₂Ni团簇表面进行需克服的活化能垒最低, 反应最易进行. Sn₁₂Ni团簇上生成碳需要较高的活化能, 说明Sn₁₂Ni团簇能够有效抑制焦碳的生成, 一定程度上克服了碳沉积导致的催化剂失活现象, 并且Sn₁₂Ni团簇在C ^*和CH ^*氧化过程中表现出最佳的催化活性. Cu₁₂Ni团簇仅在甲烷脱氢过程中表现出较为优异的催化活性.

关键词: 密度泛函理论, 合金团簇, 甲烷干法重整, 能垒

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

中图分类号:

O641
O643

TrendMD:

陈涛,方镭,罗伟,孟跃,薛继龙,夏盛杰,倪哲明. 双金属合金团簇M₁₂Ni(M=Pt, Sn, Cu)催化甲烷干法重整反应的理论研究. 高等学校化学学报, 2019, 40(10): 2135.

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) ^†. Chem. J. Chinese Universities, 2019, 40(10): 2135.

图/表 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

Table 1 Adsorption energy of 16 active species on 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

Table 1 Adsorption energy of 16 active species on 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

Fig.3 Elementary reaction of dry reforming of methane

Table 2 Activation energy(Ea) and reaction energy change(ΔE) 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 $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

Table 2 Activation energy(Ea) and reaction energy change(ΔE) 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 $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

Table 3 Activation energy(Ea) and reaction energy change(ΔE) of carbon dioxide activation processes 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

Table 3 Activation energy(Ea) and reaction energy change(ΔE) of carbon dioxide activation processes 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

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

Table 4 Activation energy(Ea) and reaction energy change(ΔE) of C* and CH* oxidation processes 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

Table 5 Activation energy(Ea) and reaction energy change(ΔE) of H2 and H2O formation processes 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

Table 5 Activation energy(Ea) and reaction energy change(ΔE) of H2 and H2O formation processes 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

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

参考文献 29

[1]	Cao P. F., Adegbite S., Zhao H. T., Lester E., Wu T. , Appl. Energ., 2018,227, 190— 197
[2]	Saché E. L., Pastor-Pérez L., Watson D., Sepúlveda-Escribano A., Reina T. R. , Appl. Catal. B:Environ., 2018,236, 458— 465
[3]	Zhu Y. A., Chen D., Zhou X. G., Yuan W. K. , Catal. Today, 2009,148, 260— 267
[4]	Fujita T., Peng X. B., Yamaguchi A., Cho Y., Zhang Y. Z. Higuchi K., Yamamoto Y., Tokunaga T., Arai S., Miyauchi M., Abe H. , ACS Omega, 2018,3(12), 16651— 16657
[5]	Newnham J., Mantri K., Amin M. H., Tardio J., Bhargava S. K. , Int. J. Hydrogen Energ., 2012,37(2), 1454— 1464
[6]	Vasconcelos B. R. D., Minh D. P., Lyczko N., Phan T. S. Sharrock P., Nzihou A. , Fuel, 2018,226, 195— 203
[7]	Fan C., Zhu Y. A., Xu Y., Zhou Y., Zhou X. G. Chen D. , J. Chem. Phys., 2012,137(1), 014703
[8]	Guharoy U., Sache E. L., Cai Q., Reina T. R., Gu S. , J. CO₂. Util., 2018,7, 1— 10
[9]	Nataj S. M. M., Alavi S. M., Mazloom G. , J. Nat. Gas. Chem., 2018,27(5), 1475— 1488
[10]	García-Diéguez M., Pieta I. S., Herrera M. C., Larrubia M. A., Alemany L. J. , J. Catal., 2010,270(1), 136— 145
[11]	Steinhauer B., Kasireddy M. R., Radnik J., Martin A. , Appl. Catal. A:Gen., 2009,366(2), 333— 341
[12]	Wu S. K., Lin R. J., Jang S., Chen H. L., Wang S. M., Li F. Y. J. Phys. Chem. C, 2014,118(1), 298— 309
[13]	Xu G. L., Zhang L., He C. Z., Ma D. W., Lu Z. S. Sensor. Actuat. B:Chem., 2015,221, 717— 722
[14]	Mahammedi N. A., Ferhat M., Belkada R. , Superlattice Microst., 2016,100, 296— 305
[15]	Ge Q., Jenkins S. J.., King D. A. , Chem. Phys. Lett., 2000,327, 125— 130
[16]	Liu J., Wen S. M., Wang Y. J., Deng J. S., Chen X. M. , Int. J. Miner. Process, 2016,147, 28— 30
[17]	Zhao F. F., Liu C., Wang P., Huang S. P. Tian H. P. , J. Alloy Compd., 2013,577, 669— 676
[18]	Fang L., Xia S. J., Xue J. L., Meng Y., Qian M. D., Luo W., Zhang X. F., Ni Z. M. , Chem. J. Chinese Universities, 2018,39(8), 1721— 1728
	( 方镭, 夏盛杰, 薛继龙, 孟跃, 钱梦丹, 罗伟, 张晓锋, 倪哲明 . 高等学校化学学报, 2018,39(8), 1721— 1728)
[19]	Jiang J. H., Cao Y. Y., Ni Z. M., Zhang L. Y. , J. Fuel Chem. Technol., 2016,44(8), 961— 969
	( 蒋军辉, 曹勇勇, 倪哲明, 张连阳 . 燃料化学学报, 2016,44(8), 961— 969)
[20]	Ham H. C., Hwang G. S., Han J., Nam S. W., Lim T. H. , J. Phys. Chem. C, 2010,114, 14922— 14928
[21]	Ray K., Bhardwaj R., Singh B., Deo G., Phys. Chem. Chem. Phys., 2018,20, 15939— 15950
[22]	Rad A. S. , Appl. Surf. Sci., 2015,357, 1217— 1224
[23]	Prats H., Gutierrez R. A., Pinero J. J., Vines F., Bromley S. T. Ramirez P. J., Rodriguez J. A., Illas F. , J. Am. Chem. Soc., 2019,141, 5303— 5313
[24]	Guharoy U., Reina T. R., Olsson E., Gu S., Cai Q. , ACS Catal., 2019,9, 3487— 3497
[25]	Xing B., Pang X. Y., Wang G. C., Shang Z. F. , J. Mol. Catal. A:Chem., 2010,315, 187— 196
[26]	Li M. R., Lu Z., Wang G. C. , Catal. Sci. Technol., 2017,7(16), 3613— 3625
[27]	Qi Q. H., Wang X. J., Chen L., Li B. T. , Appl. Surf. Sci., 2013,284, 784— 791
[28]	Liu H. Y., Zhang R. G., Yan R. X., Li J. R. , Wang B. J., Xie K. C. , Appl. Surf. Sci., 2012,258, 8177— 8184
[29]	Guo D., Wang G. C. , J. Phys. Chem. C, 2017,121(47), 26308— 26320

相关文章 15

[1]	何鸿锐, 夏文生, 张庆红, 万惠霖. 羟基氧化铟团簇与二氧化碳和甲烷作用的密度泛函理论研究[J]. 高等学校化学学报, 2022, 43(8): 20220196.
[2]	黄汉浩, 卢湫阳, 孙明子, 黄勃龙. 石墨炔原子催化剂的崭新道路:基于自验证机器学习方法的筛选策略[J]. 高等学校化学学报, 2022, 43(5): 20220042.
[3]	刘洋, 李旺昌, 张竹霞, 王芳, 杨文静, 郭臻, 崔鹏. Sc₃C₂@C₈₀与[12]CPP纳米环之间非共价相互作用的理论研究[J]. 高等学校化学学报, 2022, 43(11): 20220457.
[4]	程媛媛, 郗碧莹. ·OH自由基引发CH₃SSC $H 3 •$ ⁺自由基裂解反应机理的理论研究[J]. 高等学校化学学报, 2022, 43(10): 20220271.
[5]	周成思, 赵远进, 韩美晨, 杨霞, 刘晨光, 贺爱华. 硅烷类外给电子体对丙烯-丁烯序贯聚合的调控作用[J]. 高等学校化学学报, 2022, 43(10): 20220290.
[6]	王园月, 安梭梭, 郑旭明, 赵彦英. 5-巯基-1, 3, 4-噻二唑-2-硫酮微溶剂团簇的光谱和理论计算研究[J]. 高等学校化学学报, 2022, 43(10): 20220354.
[7]	马丽娟, 高升启, 荣祎斐, 贾建峰, 武海顺. Sc, Ti, V修饰B/N掺杂单缺陷石墨烯的储氢研究[J]. 高等学校化学学报, 2021, 42(9): 2842.
[8]	钟声广, 夏文生, 张庆红, 万惠霖. 电中性团簇MCu₂O_x(M=Cu²⁺, Ce⁴⁺, Zr⁴⁺)上甲烷和二氧化碳直接合成乙酸的理论研究[J]. 高等学校化学学报, 2021, 42(9): 2878.
[9]	黄罗仪, 翁约约, 黄旭慧, 王朝杰. 车前草中黄酮类成分结构和性质的理论研究[J]. 高等学校化学学报, 2021, 42(9): 2752.
[10]	王建, 张红星. 四配位铂磷光发射体结构与光物理性质关系的理论研究[J]. 高等学校化学学报, 2021, 42(7): 2245.
[11]	胡伟, 刘小峰, 李震宇, 杨金龙. 金刚石纳米线氮空位色心的表面与尺寸效应[J]. 高等学校化学学报, 2021, 42(7): 2178.
[12]	杨一莹, 朱荣秀, 张冬菊, 刘成卜. 金催化炔基苯并二𫫇英环化合成8-羟基异香豆素的理论研究[J]. 高等学校化学学报, 2021, 42(7): 2299.
[13]	柳扬, 李清波, 孙杰, 赵显. Ga对在AlN衬底上直接生长石墨烯的远程催化[J]. 高等学校化学学报, 2021, 42(7): 2271.
[14]	应富鸣, 计辰儒, 苏培峰, 吴玮. 基于完全活性空间自洽场的杂化多组态密度泛函方法λ-DFCAS[J]. 高等学校化学学报, 2021, 42(7): 2218.
[15]	郑若昕, 张颖, 徐昕. 低标度XYG3双杂化密度泛函的开发与测评[J]. 高等学校化学学报, 2021, 42(7): 2210.

双金属合金团簇M₁₂Ni(M=Pt, Sn, Cu)催化甲烷干法重整反应的理论研究

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 29

相关文章 15

编辑推荐

Metrics

本文评价