多孔氮化钛载体上铂催化剂的原子层沉积制备及其催化氧气还原性能

doi:10.3866/PKU.WHXB201906070

摘要/Abstract

摘要：

为有效解决铂(Pt)催化剂用于氧气还原反应(ORR)面临的催化活性及稳定性问题，本文首先合成了具有良好导电性、电化学稳定以及耐腐蚀等优点的一维多孔氮化钛(TiN)纳米管载体材料，然后使用原子层沉积技术(ALD)在TiN载体上沉积制备了Pt催化剂(ALD-Pt/TiN)，所得的Pt纳米颗粒尺寸均匀、高度分散且与TiN载体之间存在着较强的相互作用。催化氧气还原活性和稳定性测试表明，所得的ALD-Pt/TiN对ORR具有较高的催化活性，同时兼具良好的稳定性和耐久性。相比商用Pt/C，ALD-Pt/TiN的起始电位和稳态极限电流密度与其相近，半波电位则高出了20 mV，表现出优异的电催化性能。其优良的电催化性能主要归因于ALD沉积Pt纳米颗粒的高分散性，一维多孔结构TiN载体的高比表面积、良好导电性和抗腐蚀性能以及ALD-Pt与TiN载体间较强的相互作用等综合影响。本工作为设计新型高催化活性、高稳定性的Pt基催化剂提供了有益借鉴。

关键词: 多孔氮化钛, Pt纳米颗粒, 原子层沉积, 电催化, 氧气还原反应

Abstract:

The exploitation of high-performing stable oxygen reduction reaction (ORR) electrocatalysts is critical for energy storage and conversion technologies. The existing high-efficiency electrocatalysts applied to the ORR are mainly based on Pt and its alloys. Moreover, carrier catalysts are the most widely used in actual electrocatalysis. A suitable carrier not only improves the utilization rate of precious metals and the service life of the catalyst, but also serves as a co-catalyst to ameliorate the catalytic activity through a synergistic effect in the reaction. Therefore, research into Pt-based electrocatalysts mainly focuses on the precious metal Pt and the carrier. With the aim of improving the activity and durability of Pt-based catalysts for the ORR, one-dimensional porous titanium nitride (TiN) nanotubes with a large specific surface area as well as good conductivity, electrochemical stability, and corrosion resistance were prepared in this study, and then, Pt nanoparticles were deposited on the TiN-support by atomic layer deposition (ALD). ALD is a novel and simple method for the preparation of films or nanoparticles with fine control of the thickness or size, respectively. The results of X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) experiments confirmed that the Pt nanoparticles obtained by ALD (ALD-Pt/TiN) were face-centered cubic (fcc) crystals with a uniform size and were highly dispersed on the surface of TiN. X-ray spectroscopy (XPS) measurements verified that the binding energy of Pt 4f in ALD-Pt/TiN was positively shifted by 0.33 eV with respect to that of the Pt/C catalyst, indicating strong electronic interactions between the ALD-Pt nanoparticles and the TiN carriers. Linear sweep voltammetry (LSV) and cyclic voltammetry (CV) analyses revealed that ALD-Pt/TiN possessed high activity for the ORR and favorable durability. The onset potential and diffusion-limiting current density of ALD-Pt/TiN were similar to those of commercial Pt/C, while the half-wave potential was 20 mV higher than that of commercial Pt/C, indicating better electrocatalytic performance of the designed material. Furthermore, the electrocatalytic mechanism and kinetics for ALD-Pt/TiN were investigated by rotating ring-disc electrode (RRDE) experiments. The results suggested that the electron transfer number of the ALD-Pt/TiN catalyst was about 3.93, indicating that the ORR on the electrode was dominated by an efficient four-electron pathway. At the same time, the peroxide content was only 5%. The results of accelerated durability testing (ADT) showed that ALD-Pt/TiN had better ORR stability than Pt/C. This excellent electrocatalytic performance was probably due to the high dispersibility of the Pt nanoparticles deposited by ALD, good conductivity and corrosion resistance of TiN, and strong interactions between ALD-Pt and the TiN support. This work provides a reliable strategy for the design of new electrocatalytic materials with high activity and stability. Future research will focus on the strong interactions between ALD-Pt and the TiN carriers.

Key words: Porous Titanium Nitride, Platinum nanoparticles, Atomic layer deposition, Electrocatalysis, Oxygen reduction reaction

唐小龙,张盛辉,于婧,吕春晓,迟雨晴,孙君伟,宋誉,袁丁,马兆立,张立学. 多孔氮化钛载体上铂催化剂的原子层沉积制备及其催化氧气还原性能[J]. 物理化学学报, 2020, 36(7), 1906070. doi: 10.3866/PKU.WHXB201906070

Xiaolong Tang,Shenghui Zhang,Jing Yu,Chunxiao Lü,Yuqing Chi,Junwei Sun,Yu Song,Ding Yuan,Zhaoli Ma,Lixue Zhang. Preparation of Platinum Catalysts on Porous Titanium Nitride Supports by Atomic Layer Deposition and Their Catalytic Performance for Oxygen Reduction Reaction[J]. Acta Physico-Chimica Sinica 2020, 36(7), 1906070. doi: 10.3866/PKU.WHXB201906070

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201906070

https://www.whxb.pku.edu.cn/CN/Y2020/V36/I7/1906070

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参考文献 38

1	Lee J. S. ; Kim S.T. ; Cao R. ; Choi N. S. ; Liu M. ; Lee K. T. ; Cho J. Adv. Energy Mater. 2011, 1, 34. doi: 10.1002/aenm.201000010
2	Wu G. ; More K. L. ; Johnston C. M. ; Zelenay P. Science 2011, 332, 443. doi: 10.1126/science.1200832
3	Dai L. ; Xue Y. ; Qu L. ; Choi H. J. ; Baek J. B. Chem. Rev. 2015, 115, 4823. doi: 10.1021/cr5003563
4	Van Pham C. ; Klingele M. ; Britton B. ; Vuyyuru K. R. ; Unmuessig T. ; Holdcroft S. ; Fischer A. ; Thiele S. Adv. Sustainable Syst. 2017, 1, 1600038. doi: 10.1002/adsu.201600038
5	Lee J. S. ; Nam G. ; Sun J. ; Higashi S. ; Lee H. W. ; Lee S. ; Chen W. ; Cui Y. ; Cho J. Adv. Energy Mater. 2016, 6, 1601052. doi: 10.1002/aenm.201601052
6	Wang B. ; Cui X. ; Huang J. ; Cao R. ; Zhang Q. Chin. Chem. Lett. 2018, 29, 1757d. doi: 10.1016/j.cclet.2018.11.021
7	Cheng N. ; Li H. ; Li G. ; Lv H. ; Mu S. ; Sun X. ; Pan M. Chem. Commun. 2011, 47, 12792. doi: 10.1039/C1CC15203C
8	Stephens I. E. ; Bondarenko A. S. ; Gronbjerg U. ; Rossmeisl J. ; Chorkendorff I. Energy Environ. Sci. 2012, 5, 6744. doi: 10.1039/C2EE03590A
9	Ramli Z. ; Kamarudin S. K. Nanoscale Res. Lett. 2018, 13, 410. doi: 10.1186/s11671-018-2799-4
10	Antolini E. Int. J. Energy Res. 2018, 42, 3747. doi: 10.1002/er.4134
11	Luo M. C. ; Sun Y. J. ; Qin Y. N. ; Yang Y. ; Wu D. ; Guo S. J. Acta Phys. -Chim. Sin. 2018, 34, 361. doi: 10.3866/PKU.WHXB201708312
	骆明川; 孙英俊; 秦英楠; 杨勇; 吴冬; 郭少军. 物理化学学报, 2018, 34, 361. doi: 10.3866/PKU.WHXB201708312
12	Chang Q.W. ; Xiao F. ; Xu Y. ; Shao M. H. Acta Phys. -Chim. Sin. 2017, 33, 9. doi: 10.3866/PKU.WHXB201609202
	常乔婉; 肖菲; 徐源; 邵敏华. 物理化学学报, 2017, 33, 9. doi: 10.3866/PKU.WHXB201609202
13	Sui S. ; Wang X. ; Zhou X. ; Su Y. ; Riffat S. ; Liu C. J. J. Mater. Chem. A 2017, 5, 1808. doi: 10.1039/C6TA08580F
14	Khalily M. A. ; Patil B. ; Yilmaz E. ; Uyar T. Nanoscale Adv. 2019, 55, 1225. doi: 10.1039/C8NA00330K
15	Hsu I. J. ; Hansgen D. A. ; McCandless B. E. ; Willis B. G. ; Chen J. G. J. Phys. Chem. C 2011, 115, 3709. doi: 10.1021/jp111180e
16	Cheng N. ; Banis M. N. ; Liu J. ; Riese A. ; Mu S. ; Li R. ; Sham T. K. ; Sun X. Energy Environ. Sci. 2015, 8, 1450. doi: 10.1039/C4EE04086D
17	Shu T. ; Liao S. J. ; Hsieh C. T. ; Roy A. K. ; Liu Y. Y. ; Tzou D. Y. ; Chen W. Y. Electrochim. Acta 2012, 75, 101. doi: 10.1016/j.electacta.2012.04.084
18	Dasgupta N. P. ; Liu C. ; Andrews S. ; Prinz F. B. ; Yang P. J. Am. Chem. Soc. 2013, 135, 12932. doi: 10.1021/ja405680p
19	Zhang J. ; Yu Z. ; Gao Z. ; Ge H. ; Zhao S. ; Chen C. ; Chen S. ; Tong X. ; Wang M. ; Zheng Z. ; et al Angew. Chem. Int. Ed. 2017, 56, 816. doi: 10.1002/anie201611137
20	Cargnello M. ; Doan Nguyen V. V. ; Gordon T. R. ; Diaz R. E. ; Stach E. A. ; Gorte R. J. Science 2013, 341, 771. doi: 10.1126/science.1240148
21	Tian X. L. ; Luo J. ; Nan H. ; Zou H. ; Chen R. ; Shu T. ; Li X. ; Li Y. ; Song H. ; Liao S. J. Am. Chem. Soc. 2016, 138, 1575. doi: 10.1021/jacs.5b11364
22	Ottakam Thotiyl M.O. ; Ravikumar T. ; Sampath S. J. Mater. Chem. 2010, 20, 10643. doi: 10.1039/C0JM01600D
23	Yang M. ; Cui Z. ; Di Salvo F. J. Phys. Chem. Chem. Phys. 2013, 15, 1088. doi: 10.1039/C2CP44215A
24	Wang Y. J. ; Wilkinson D. P. ; Zhang J. Chem. Rev. 2011, 111, 7625. doi: 10.1021/cr100060r
25	Xiao Y. ; Zhan G. ; Fu Z. ; Pan Z. ; Xiao C. ; Wu S. ; Chen C. ; Hu G. ; Wei Z. J. Power Sources 2015, 284, 296. doi: 10.1016/j.jpowsour.2015.03.001
26	Luo J. ; Tang H. ; Tian X. ; Hou S. ; Li X. ; Du L. ; Liao S. ACS Appl. Mater. Interface 2018, 10, 3530. doi: 10.1021/acsami.7b15159
27	Shin H. ; Kim H. I. ; Chung D. Y. ; Yoo J. M. ; Weon S. ; Choi W. ; Sung Y. E. ACS Catal. 2016, 6, 3914. doi: 10.1021/acscatal.6b00384
28	Zhu X. ; Yang X. ; Lv C. ; Guo S. ; Li J. ; Zheng Z. ; Zhu H. ; Yang D. ACS Appl. Mater. Interfaces 2016, 8, 18815. doi: 10.1021/acsami.6b04588
29	Li C. ; Tan H. ; Lin J. ; Luo X. ; Wang S. ; You J. ; Kang Y. -M. ; Bando Y. ; Yamauchi Y. ; Kim J. Nano Today 2018, 21, 91. doi: 10.1016/j.nantod.2018.06.005
30	Zhang N. ; Zhang S. ; Du C. ; Wang Z. ; Shao Y. ; Kong F. ; Lin Y. ; Yin G. Electrochim. Acta 2014, 117, 413. doi: 10.1016/j.electacta.2013.11.139
31	Seifitokaldani A. ; Savadogo O. ; Perrier M. Electrochim. Acta 2014, 141, 25. doi: 10.1016/j.electacta.2014.07.027
32	Nie Y. ; Li L. ; Wei Z. Chem. Soc. Rev. 2015, 44, 2168. doi: 10.1039/C4CS00484A
33	Bai Q. ; Shen F. C. ; Li S. L. ; Liu J. ; Dong L. Z. ; Wang Z. M. ; Lan Y. Q. Small Methods 2018, 2, 1800049. doi: 10.1002/smtd.201800049
34	Liu C. ; Wang J. ; Li J. ; Liu J. ; Wang C. ; Sun X. ; Shen J. ; Han W. ; Wang L. J. Mater. Chem. A 2017, 5, 1211. doi: 10.1039/C6TA09193H
35	Marković N. M. ; Schmidt T. J. ; Stamenković V. ; Ross P. N. Fuel Cells 2001, 1, 105. doi: 10.1002/1615-6854[200107
36	Zhao Y. ; Lai Q. ; Zhu J. ; Zhong J. ; Tang Z. ; Luo Y. ; Liang Y. Small 2018, 14, 1704207. doi: 10.1002/smtd.201800049
37	Kulkarni A. ; Siahrostami S. ; Patel A. ; Nørskov J. K. Chem. Rev. 2018, 118, 2302. doi: 10.1021/acs.chemrev.7b00488
38	Cui Z. ; Yang M. ; Chen H. ; Zhao M. ; DiSalvo F. J. ChemSusChem 2014, 7, 3356. doi: 10.1002/cssc.201402726

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