PtFe掺杂石墨烯抗CO中毒性能的理论研究

doi:10.7503/cjcu20170415

摘要/Abstract

摘要：

基于密度泛函理论第一性原理研究了以单空位缺陷(SV)石墨烯为载体的Pt, Fe及PtFe二元金属催化剂的抗CO中毒能力. 结果表明, 对于单金属原子Pt和Fe, Fe更易吸附在SV石墨烯上; 而对于PtFe二元金属催化剂, SV石墨烯对其固定能力明显好于Pt-SV, 即Pt催化剂中掺杂Fe大大增加了SV石墨烯对金属催化剂的稳定性. Pt, Fe及PtFe二元金属催化剂抗CO中毒能力的研究结果表明, PtFe-6结构的抗CO中毒能力明显强于Pt-SV, 接近于Fe-SV的抗CO中毒能力, 在所有二元金属催化剂中PtFe-6的稳定性最好, 明显优于Pt在SV石墨烯上的稳定性. 通过在Pt中加入非贵金属Fe既可提高DMFC中阳极Pt催化剂的抗CO中毒能力, 又可提高其催化活性.

关键词: 密度泛函理论, 铂铁二元金属, 单空位缺陷石墨烯, 抗一氧化碳中毒

Abstract:

The anti-CO poisoning ability of Pt, Fe and PtFe binary metal catalysts with single-vacancy defect(SV) graphene as carrier was studied based on the density functional theory(DFT). For the single metal atoms Pt and Fe, Fe is more easily adsorbed on SV graphene. For PtFe binary metal catalyst, SV graphene has a tendency to further strengthen its stability. The anti-CO poisoning ability of PtFe-6 structure is better than Pt-SV, and is more close to the anti-CO poisoning ability of Fe-SV. PtFe-6 is also the most stable among all binary metal catalysts, close to the Fe adsorption on the SV graphene. Therefore, the anti-CO poisoning ability of anodic Pt catalyst in DMFC can be improved by adding non-noble metal Fe in Pt, and its catalytic activity can also be enhanced.

Key words: Density functional theory, PtFe binary metal, Single-vacancy defect(SV) graphene, Anti-CO poisoning

中图分类号:

O641

TrendMD:

佟永纯, 王清云, 王永成, 唐琳. PtFe掺杂石墨烯抗CO中毒性能的理论研究. 高等学校化学学报, 2017, 38(12): 2213.

TONG Yongchun, WANG Qingyun, WANG Yongcheng, TANG Lin. Theoretical Study on the Anti-CO Poisoning Performance of PtFe Doped Graphene^†. Chem. J. Chinese Universities, 2017, 38(12): 2213.

图/表 5

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System	r(M—C_sur)/nm	r(Pt-Fe)/nm	q_M/e	E_ads/eV
Pt-SV	0.206, 0.206, 0.206		+0.349	4.31
Fe-SV	0.178, 0.178, 0.178		+0.404	7.81
PtFe-1	0.207, 0.208, 0.209, 0.209	0.263	+0.249, +0.278	4.21
PtFe-2	0.207, 0.207, 0.201, 0.231	0.266	+0.153, +0.249	3.75
PtFe-3	0.207, 0.207, 0.207	0.256	+0.178, +0.062	3.86
PtFe-4	0.178, 0.178, 0.180	0.259	+0.061, +0.397	6.94
PtFe-5	0.177, 0.180, 0.177	0.267	+0.112, +0.360	6.89
PtFe-6	0.178, 0.178, 0.178	0.250	-0.069, +0.457	6.99

System	r(M—C_sur)/nm	r(Pt-Fe)/nm	q_M/e	E_ads/eV
Pt-SV	0.206, 0.206, 0.206		+0.349	4.31
Fe-SV	0.178, 0.178, 0.178		+0.404	7.81
PtFe-1	0.207, 0.208, 0.209, 0.209	0.263	+0.249, +0.278	4.21
PtFe-2	0.207, 0.207, 0.201, 0.231	0.266	+0.153, +0.249	3.75
PtFe-3	0.207, 0.207, 0.207	0.256	+0.178, +0.062	3.86
PtFe-4	0.178, 0.178, 0.180	0.259	+0.061, +0.397	6.94
PtFe-5	0.177, 0.180, 0.177	0.267	+0.112, +0.360	6.89
PtFe-6	0.178, 0.178, 0.178	0.250	-0.069, +0.457	6.99

System	r(C—O)/nm	r(M-CO)/nm	r(M—C_sur)/nm	q_M/e	E_ads/eV
Pt-SV-CO	0.115	0.216	0.206,0.212,0.212	+0.234	1.41
Fe-SV-CO	0.116	0.187	0.181	+0.323	0.89
PtFe1-CO	0.115	0.210	0.209,0.215,0.214,0.209	+0.132,+0.348	1.12
PtFe2-CO-a	0.115	0.211	0.208,0.214,0.214,0.224	+0.063,+0.353	1.46
PtFe2-CO-b	0.117	0.176	0.206,0.206,0.208,0.213	+0.250,+0.245	2.31
PtFe3-CO	0.117	0.182	0.205,0.206,0.211	+0.107,+0.259	1.63
PtFe4-CO-a	0.115	0.198	0.178,0.179,0.178	+0.039,+0.392	1.63
PtFe4-CO-b	0.178	0.197,0.111	0.178,0.179,0.183	+0.186, +0.436	1.93
PtFe5-CO	0.115	0.198	0.177,0.178,0.179	+0.046,+0.374	1.71
PtFe6-CO	0.115	0.208	0.177,0.178,0.178	-0.088,+0.433	0.93

System	r(C—O)/nm	r(M-CO)/nm	r(M—C_sur)/nm	q_M/e	E_ads/eV
Pt-SV-CO	0.115	0.216	0.206,0.212,0.212	+0.234	1.41
Fe-SV-CO	0.116	0.187	0.181	+0.323	0.89
PtFe1-CO	0.115	0.210	0.209,0.215,0.214,0.209	+0.132,+0.348	1.12
PtFe2-CO-a	0.115	0.211	0.208,0.214,0.214,0.224	+0.063,+0.353	1.46
PtFe2-CO-b	0.117	0.176	0.206,0.206,0.208,0.213	+0.250,+0.245	2.31
PtFe3-CO	0.117	0.182	0.205,0.206,0.211	+0.107,+0.259	1.63
PtFe4-CO-a	0.115	0.198	0.178,0.179,0.178	+0.039,+0.392	1.63
PtFe4-CO-b	0.178	0.197,0.111	0.178,0.179,0.183	+0.186, +0.436	1.93
PtFe5-CO	0.115	0.198	0.177,0.178,0.179	+0.046,+0.374	1.71
PtFe6-CO	0.115	0.208	0.177,0.178,0.178	-0.088,+0.433	0.93