ORR催化剂Nim@Pt1Aun-m-1 (n = 19, 38, 55, 79; m = 1, 6, 13, 19)的密度泛函研究

doi:10.13208/j.electrochem.210329

摘要/Abstract

摘要：

燃料电池的阴极反应的反应动力学速率非常慢,限制了燃料电池技术的发展。因此,寻找低成本、高活性的氧还原催化剂具有重要的意义。多元金属核壳团簇表现出优良的氧还原活性。在本文中,以原子个数为19、38、55和79的八面体团簇作催化剂模型,采用密度泛函理论(GGA-PBE-PAW)方法,研究了一系列不同尺寸核壳Ni_m@M_n_-_m (n = 19, 38, 55, 79;m = 1, 6, 13, 19; M = Pt, Pd, Cu, Au, Ag)团簇催化剂的活性规律。优化*O、*OH和*OOH吸附中间体结构,计算了吸附自由能和反应吉布斯自由能,以超电势为催化活性的描述符,研究了单原子Pt嵌入Ni_m@Au_n_-_m团簇的活性规律。结果表明,Ni₆@Pt₁Au₃₁具有最好的ORR活性,并且Ni₁@Pt₁Au₁₇、Ni₆@Pt₁Au₃₁、Ni₁₃@Pt₁Au₄₁、Ni₁₉@Pt₁Au₅表现出比Pt₃₈团簇以及Pt(111)表面更高的催化活性。Bader电荷和态密度分析表面,核壳之间的电荷转移以及单原子Pt嵌入Ni_m@Au_n_-_m表面,改变了吸附位的电子性质,降低了*OH的吸附强度,提高了ORR活性。单原子Pt嵌入Ni_m@Au_n_-_m表面可能是一种合适的多元金属核壳ORR催化剂设计策略。

关键词: 核壳金属团簇, 氧还原反应, 密度泛函理论, 超电势, 单原子催化

Abstract:

The slow kinetics of oxygen reduction reaction (ORR) limits the performance of low temperature fuel cells. Thus, it needs to design effective catalysts with low cost. Core-shell clusters (CSNCs) show promising activity because of their size-dependent geometric and electronic effects. The ORR activity trend of Ni_m@Pt₁Au_n_-_m_-1(n = 19, 38, 55, 79; m = 1, 6, 13, 19) was studied using the GGA-PBE-PAW methods. The adsorption configurations of *O, *OH and *OOH were optimized and the reaction free energies of four proton electron (H⁺ + e^-) transfer steps were calculated. Using overpotential as a descriptor for the catalytic activity, Ni₆@Pt₁Au₃₁ was found to be the most active ORR catalyst. Ni₁@Pt₁Au₁₇, Ni₁₃@Pt₁Au₄₁, and Ni₁₉@Pt₁Au₅₉ had better activity than pure Pt clusters and Pt(111). Bader charge and DOS data indicate that the single Pt atom embedded on Ni_m@Au_n_-_m can tune the electronic property of active site, and thus, significantly improve the activity. The present study showed that the single Pt atom embedded on Ni_m@Au_n_-_m is a rational strategy to design effective core-shell ORR catalysts.

Key words: core-shell metal clusters, oxygen reduction reaction, density functional theory, overpotential, single atom catalysis

李文杰, 田东旭, 杜红, 燕希强. ORR催化剂Ni_m@Pt₁Au_n_-_m_-1(n = 19, 38, 55, 79; m = 1, 6, 13, 19)的密度泛函研究[J]. 电化学（中英文）, 2021, 27(4): 357-365.

Wen-Jie Li, Dong-Xu Tian, Hong Du, Xi-Qiang Yan. DFT Study of Ni_m@Pt₁Au_n_-_m_-1(n=19, 38, 55, 79; m = 1, 6, 13, 19) Core-Shell ORR Catalyst[J]. Journal of Electrochemistry, 2021, 27(4): 357-365.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.210329

https://electrochem.xmu.edu.cn/CN/Y2021/V27/I4/357

图/表 10

Figure 1

Table 1

Figure 2

Table 2

Figure 3

Table 3

Figure 4

Figure 5

Figure 6

Figure 7

参考文献 45

[1]	Antolini E, Passos R R, Ticianelli E A. Electrocatalysis of oxygen reduction on a carbon supported platinum-vanadium alloy in polymer electrolyte fuel cells[J]. Electrochim. Acta., 2002, 48(3): 263-270. doi: 10.1016/S0013-4686(02)00644-8 URL
[2]	Gasteiger H A, Kocha S S, Sompalli B, Wagner F T. Activity benchmarks for Pt, Pt-alloy and non-Pt oxygen reduction catalysts for PEMFCs[J]. Appl. Catal. B - Environ., 2005, 56(1-2): 9-35. doi: 10.1016/j.apcatb.2004.06.021 URL
[3]	Debe M K. Electrocatalyst approaches and challenges for automotive fuel cells[J]. Nature, 2012, 486(7401): 43-51. doi: 10.1038/nature11115 URL
[4]	Chen J, Lim B, Lee E P, Xia Y. Shape-controlled synjournal of platinum nanocrystals for catalytic and electrocatalytic applications[J]. Nano Today, 2009, 4(1): 81-95. doi: 10.1016/j.nantod.2008.09.002 URL
[5]	Guo S J, Wang E K. Noble metal nanomaterials: Controllable synjournal and application in fuel cells and analytical sensors[J]. Nano Today, 2011, 6(3): 240-264. doi: 10.1016/j.nantod.2011.04.007 URL
[6]	Koenigsmann C, Santulli A C, Gong K, Vukmirovic M B, Zhou W P, Sutter E, Wong S S, Adzic R R. Enhanced electrocatalytic performance of processed, ultrathin, supported Pd-Pt core-shell nanowire catalysts for the oxygen reduction reaction[J]. J. Am. Chem. Soc., 2011, 133(25): 9783-9795. doi: 10.1021/ja111130t URL
[7]	Koenigsmann C, Sutter E, Chiesa T A, Adzic R R, Wong S S. Highly enhanced electrocatalytic oxygen reduction performance observed in bimetallic palladium-based nano-wires prepared under ambient, surfactantless conditions[J]. Nano Lett., 2012, 12(4): 2013-2020. doi: 10.1021/nl300033e URL
[8]	Sun S H, Zhang G X, Geng D S, Chen Y G, Li R Y, Cai M, Sun X L. A highly durable platinum nanocatalyst for proton exchange membrane fuel cells: multiarmed starlike nanowire single crystal[J]. Angew. Chem. Int. Ed., 2010, 50(2): 422-426. doi: 10.1002/anie.201004631 URL
[9]	Yang P. Platinum-based electrocatalysts with core-shell nanostructures[J]. Angew. Chem. Int. Ed., 2011, 50(12): 2674-2676. doi: 10.1002/anie.v50.12 URL
[10]	Strasser P, Koh S, Anniyev T, Greeley J, Nilsson A. Lattice-strain control of the activity in dealloyed core-shell fuel cell catalysts[J]. Nature Chem., 2010, 2(6): 454-460. doi: 10.1038/nchem.623 URL
[11]	Guo S J, Zhang S, Sun S H. Tuning nanoparticle catalysis for the oxygen reduction reaction[J]. Angew. Chem. Int. Ed., 2013, 52(33): 8526-8544. doi: 10.1002/anie.201207186 URL
[12]	Mani P, Srivastava R, Strasser P. Dealloyed PtCu coreshell nanoparticle electrocatalysts for use in PEM fuel cell cathodes[J]. J. Phys. Chem. C, 2012, 112(7): 2770-2778. doi: 10.1021/jp0776412 URL
[13]	Wang D L, Xin H L L, Hovden R, Wang H S, Yu Y C, Muller D A, Disalvo F J, Abrua H C. Structurally ordered intermetallic platinum-cobalt core-shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts[J]. Nat. Mater., 2012, 12(1): 81-87. doi: 10.1038/nmat3458 URL
[14]	Wang G X, Wu H M, Wexler D, Liu H K, Savadogo O. Ni@Pt core-shell nanoparticles with enhanced catalytic activity for oxygen reduction reaction[J]. J. Alloy. Compd., 2010, 503(1): L1-L4. doi: 10.1016/j.jallcom.2010.04.236 URL
[15]	Neergat M, Rahul R. Unsupported Cu-Pt core-shell nano-particles: Oxygen reduction reaction (ORR) catalyst with better activity and reduced precious metal content[J]. J. Electrochem. Soc., 2012, 159(7): F234-F241. doi: 10.1149/2.039207jes URL
[16]	Jang J H, Lee E, Park J, Kim G, Hong S, Kwon Y U. Rational syntheses of core-shell Fex@Pt nanoparticles for the study of electrocatalytic oxygen reduction reaction[J]. Sci. Rep., 2013, 3: 2872. doi: 10.1038/srep02872 URL
[17]	Chen Y M, Liang Z X, Yang F, Liu Y W, Chen S L. Ni-Pt core-shell nanoparticles as oxygen reduction electrocatalysts: Effect of Pt shell coverage[J]. J. Phys. Chem. C, 2011, 115(49): 24073-24079. doi: 10.1021/jp207828n URL
[18]	Zhang Y F, Qin J, Leng D Y, Liu Q R, Xu X Y, Yang B, Yin F. Tunable strain drives the activity enhancement for oxygen reduction reaction on Pd@Pt core-shell electrocatalysts[J]. J. Power Sources, 2021, 485: 229340. doi: 10.1016/j.jpowsour.2020.229340 URL
[19]	Park J, Zhang L, Choi S I, Roling L T, Lu N, Herron J A, Xie S F, Wang J G, Kim M J, Mavrikakis M, Xia Y N. Atomic layer-by-layer deposition of platinum on palladium octahedra for enhanced catalysts toward the oxygen reduction reaction[J]. ACS Nano, 2015, 9(3): 2635-2647. doi: 10.1021/nn506387w URL
[20]	Zhang L, Iyyamperumal R, Yancey D F, Crooks R M, Henkelman G. Design of Pt-shell nanoparticles with alloy cores for the oxygen reduction reaction[J]. ACS Nano, 2013, 7(10): 9168-9172. doi: 10.1021/nn403788a URL
[21]	Strasser P, Koh S, Anniyev T, Greeley J, More K, Yu C, Liu Z, Kaya S, Nordlund D, Ogasawara H, Toney M F, Nilsson A. Lattice-strain control of the activity in dealloyed core-shell fuel cell catalysts[J]. Nat. Chem., 2010, 2(6): 454-460. doi: 10.1038/nchem.623 URL
[22]	Zhang J L, Vukmirovic M B, Sasaki K, Nilekar A U, Ma-vrikakis M, Adzic R R. Mixed-metal Pt monolayer electrocatalysts for enhanced oxygen reduction kinetics[J]. J. Am. Chem. Soc., 2005, 127(36): 12480-12481. doi: 10.1021/ja053695i URL
[23]	Nörskov J K, Rossmeisl J, Logadottir A, Lindqvist L, Kitchin J R, Bligaard T, Jónsson H. Origin of the overpotential for oxygen reduction at a fuel-cell cathode[J]. J. Phys. Chem. B, 2004, 108(46): 17886-17892. doi: 10.1021/jp047349j URL
[24]	Cheng D J, Qiu X G, Yu H Y. Enhancing oxygen reduction reaction activity of Pt-shelled catalysts via subsurface alloying[J]. Phys. Chem. Chem. Phys., 2014, 16(38): 20377-20381. doi: 10.1039/C4CP02863E URL
[25]	Wang L L, Johnson D D. Predicted trends of core-shell preferences for 132 late transition-metal binary-alloy nanoparticles[J]. J. Am. Chem. Soc., 2009, 131(39): 14023-14029. doi: 10.1021/ja903247x URL
[26]	Shin J, Choi J H, Cha P R, Kim S K, Kim I, Lee S C, Jeong D S. Catalytic activity for oxygen reduction reaction on platinum-based core-shell nanoparticles: All-electron density functional theory[J]. Nanoscale, 2015, 7(38): 15830-15839. doi: 10.1039/C5NR04706D URL
[27]	Nair A, Pathak B. Computational screening for ORR activity of 3d transition metal based M@Pt core-shell clusters[J]. J. Phys. Chem. C, 2019, 127(6): 3634-3644.
[28]	Greeley J, Stephens I E L, Bondarenko A S, Johansson T P, Hansen H A, Jaramillo T F, Rossmeisl J, Chorkendorff I, Nørskov J K. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts[J]. Nat. Chem., 2009, 1(7): 552-556. doi: 10.1038/nchem.367 URL
[29]	Bligaard T, Norskov J K, Dahl S, Matthiesen J, Christensen C H, Sehested J. The Brnsted-Evans-Polanyi relation and the volcano curve in heterogeneous catalysis[J]. J. Catal., 2004, 224(1): 206-217. doi: 10.1016/j.jcat.2004.02.034 URL
[30]	Sobrinho D G, Nomiyama R K, Chaves A S, Piotrowski M J, Silva J. Structure, electronic, and magnetic properties of binary Pt_nTM₅₅-_n (TM = Fe, Co, Ni, Cu, Zn) nano-clusters: A density functional theory investigation[J]. J. Phys. Chem. C, 2015, 119(27): 15669-15679. doi: 10.1021/acs.jpcc.5b02242 URL
[31]	Kresse G, Hafner J. Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium[J]. Phys. Rev. B, 1994, 49(20): 14251-14269. doi: 10.1103/PhysRevB.49.14251 URL
[32]	Kresse G G, Furthmüller J J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set[J]. Phys. Rev. B, 1996, 54(16): 11169-11186. doi: 10.1103/PhysRevB.54.11169 URL
[33]	Perdew J P, Yue W. Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation[J]. Phys. Rev. B, 1986, 33(12): 8800-8802. doi: 10.1103/PhysRevB.33.8800 URL
[34]	Perdew J P, Chevary J A, Vosko S H, Jackson K A, Pederson M R, Singh D J, Fiolhais C. Erratum: Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation[J]. Phys. Rev. B, 1993, 46(11): 6671-6687. doi: 10.1103/PhysRevB.46.6671 URL
[35]	Kresse G, Joubert D. From ultrasoft pseudopotentials to the projector augmented-wave method[J]. Phys. Rev. B, 1999, 59(3): 1758-1775. doi: 10.1103/PhysRevB.59.1758 URL
[36]	Teter M P, Payne M C, Allan D C. Solution of Schröding-er’s equation for large systems[J]. Phys. Rev. B, 1989, 40(18): 12255-12263. doi: 10.1103/PhysRevB.40.12255 URL
[37]	Grimme S. Accurate description of van der Waals complexes by density functional theory including empirical corrections[J]. J. Comput. Chem., 2004, 25(12): 1463-1473. doi: 10.1002/(ISSN)1096-987X URL
[38]	Lee K, Murray Amonn D, Kong L, Lundqvist B I, Langreth D C. A higher-accuracy van der waals density functional[J]. Phys. Rev. B, 2010, 82(8): 081101. doi: 10.1103/PhysRevB.82.081101 URL
[39]	Henkelman G, Arnaldsson A, Jónsson H. A fast and robust algorithm for Bader decomposition of charge density[J]. Comput. Mater. Sci., 2006, 36(3): 354-360. doi: 10.1016/j.commatsci.2005.04.010 URL
[40]	Grgur B N, Markovi N M, Ross P N. Temperature-dependent oxygen electrochemistry on platinum low-index single crystal surfaces in acid solutions[J]. Can. J. Chem., 1997, 75(11): 1465-1471. doi: 10.1139/v97-176 URL
[41]	Blizanac B B, Lucas C A, Gallagher M E, Arenz M, Ross P N, Markovic N M. Anion adsorption, CO oxidation, and oxygen reduction reaction on a Au(100) surface: The pH effect[J]. J. Phys. Chem. B, 2004, 108(2): 625-634. doi: 10.1021/jp036483l URL
[42]	Wang L, Zeng Z H, Ma C, Liu Y F, Giroux M, Chi M F, Jin J, Greeley J, Wang C. Plating precious metals on nonprecious metal nanoparticles for sustainable electrocatalysts[J]. Nano Lett., 2017, 17(6): 3391-3395. doi: 10.1021/acs.nanolett.7b00046 URL
[43]	Fang P P, Duan S, Lin X D, Anema J R, Li J F, Buriez O, Ding Y, Fan F R, Wu D Y, Ren B, Wang Z L, Amatore C, Tian Z Q. Tailoring Au-core Pd-shell Pt-cluster nanoparticles for enhanced electrocatalytic activity[J]. Chem. Sci., 2011, 2(3): 531-539. doi: 10.1039/C0SC00489H URL
[44]	Dinesh B, Jyh-Pin C, Che Y, Hu A, Yang Y T, Chen T Y. Programming ORR Activity of Ni/NiO_x@Pd electrocatalysts via controlling depth of surface-decorated atomic Pt clusters[J]. ACS Omega, 2018, 3(8): 8733-8744. doi: 10.1021/acsomega.8b01234 URL
[45]	Wang H, An W. Promoting the oxygen reduction reaction with gold at step/edge sites of Ni@AuPt core-shell nano-particles[J]. Catal. Sci. Technol., 2017, 7(3): 596-606. doi: 10.1039/C6CY02344D URL

System	ΔG₁/eV	ΔG₂/eV	ΔG₃/eV	ΔG₄/eV
Pt₁₉	-3.09	-0.95	-1.89	1.01
Pt₃₈	-2.47	-1.74	-1.14	0.42
Pt₅₅	-2.57	-1.67	-1.17	0.49
Pt₇₉	-2.23	-1.85	-1.08	0.24
Pt(111)	-1.80	-1.96	-0.96	-0.20

System	ΔG₁/eV	ΔG₂/eV	ΔG₃/eV	ΔG₄/eV
Pt₃₈	-2.47	-1.74	-1.14	0.42
Ni₆@Pd₃₂	-1.93	-1.91	-1.11	0.03
Ni₆@Pt₃₂	-2.10	-1.79	-1.02	0.01
Ni₆@Cu₃₂	-2.70	-1.63	-1.50	0.91
Ni₆@Au₃₂	-1.66	-1.58	-2.13	0.45
Ni₆@Ag₃₂	-2.58	-1.17	-1.96	0.79
Pt(111)	-1.80	-1.96	-0.96	-0.2

System	ΔG₁/eV	ΔG₂/eV	ΔG₃/eV	ΔG₄/eV
Pt₃₈	-2.47	-1.74	-1.14	0.42
Ni₆@Pt₁Pd₃₁	-1.81	-1.76	-1.34	-0.01
Ni₆@Pt₁Cu₃₁	-2.05	-2.01	-0.49	-0.38
Ni₆@Pt₁Au₃₁	-1.52	-1.01	-1.61	-0.77
Ni₆@Pt₁Ag₃₁	-2.92	-0.23	-1.56	-0.21
Pt(111)	-1.80	-1.96	-0.96	-0.20

ORR催化剂Ni_m@Pt₁Au_n_-_m_-1(n = 19, 38, 55, 79; m = 1, 6, 13, 19)的密度泛函研究

DFT Study of Ni_m@Pt₁Au_n_-_m_-1(n=19, 38, 55, 79; m = 1, 6, 13, 19) Core-Shell ORR Catalyst

RichHTML

PDF (PC)

补充材料

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 45

相关文章 15

Metrics

[1]	郑天龙, 欧明玉, 徐松, 毛信表, 王释一, 和庆钢. 一体式可再生燃料电池双功能氧催化剂的研究进展[J]. 电化学（中英文）, 2023, 29(7): 2205301-.
[2]	刘思淼, 周景娇, 季世军, 文钟晟. FeNi-CoP/NC双功能催化剂的制备及电催化性能研究[J]. 电化学（中英文）, 2023, 29(10): 211118-.
[3]	郭鸿波, 王亚妮, 郭凯, 雷海涛, 梁作中, 张学鹏, 曹睿. 吸电子和亲水性Co-卟啉促进电催化氧还原反应的研究[J]. 电化学（中英文）, 2022, 28(9): 2214002-.
[4]	张天恩, 颜雅妮, 张俊明, 瞿希铭, 黎燕荣, 姜艳霞. 调控Pt₃Zn合金化程度改善酸性氧还原活性与稳定性[J]. 电化学（中英文）, 2022, 28(4): 2106091-.
[5]	冯雅辰, 王翔, 王宇琪, 严会娟, 王栋. 电催化氧还原反应的原位表征[J]. 电化学（中英文）, 2022, 28(3): 2108531-.
[6]	袁会芳, 张越, 翟兴吾, 胡立兵, 葛桂贤, 王刚, 于锋, 代斌. 氮掺杂碳原位锚定铜纳米颗粒用于高效氧还原反应催化剂[J]. 电化学（中英文）, 2021, 27(6): 671-680.
[7]	林华, 吴艺津, 李君涛, 周尧. 一锅法制备Fe₂O₃@Fe-N-C氧还原电催化剂及其锌-空气电池的性能研究[J]. 电化学（中英文）, 2021, 27(4): 366-376.
[8]	吴志鹏, 钟传建. 钯基氧还原和乙醇氧化反应电催化剂:关于结构和机理研究的一些近期见解[J]. 电化学（中英文）, 2021, 27(2): 144-156.
[9]	秦雪苹, 朱尚乾, 张露露, 孙书会, 邵敏华. 酸性和碱性溶液中金属氮碳材料氧还原和氢析出反应的理论研究[J]. 电化学（中英文）, 2021, 27(2): 185-194.
[10]	蔡转运, 刘佳, 关思远, 吴德印, 田中群. 紫罗碱衍生物分子结的电学性质理论研究[J]. 电化学（中英文）, 2021, 27(1): 92-99.
[11]	徐明俊, 刘杰, 葛君杰, 刘长鹏, 邢巍. 长春应化所金属氮碳氧还原催化剂的研究进展[J]. 电化学（中英文）, 2020, 26(4): 464-473.
[12]	徐能能, 乔锦丽. 锌-空气电池双功能催化剂研究进展[J]. 电化学（中英文）, 2020, 26(4): 531-562.
[13]	杨智, 沈亚云, 周娥, 魏成玲, 秦好丽, 田娟. 前驱体中N含量对FeN/C催化剂氧还原活性的影响研究[J]. 电化学（中英文）, 2020, 26(1): 130-135.
[14]	梁栋, 房恒义, 姚硕, 于洁玫, 张昭良, 姜占坤, 高学平, 黄太仲. 不同结构及氮掺杂NiO/rGO氧还原催化剂的制备与性能研究[J]. 电化学（中英文）, 2019, 25(5): 589-600.
[15]	张利华, 陈峻峰, 黄皖唐, 胡勇有, 程建华, 陈元彩. Cu-bipy-BTC衍生碳基材料的制备及其氧还原电催化性能[J]. 电化学（中英文）, 2019, 25(4): 511-521.