Pt@Au/Al2O3核壳纳米粒子的制备和表征及其在催化氧化甲苯中的应用

doi:10.3866/PKU.WHXB201907057

摘要/Abstract

摘要：

采用种子生长法，在不存在保护剂和结构导向剂的情况下，成功制备Pt@Au核壳结构纳米颗粒，即在Pt纳米颗粒表面，AuCl⁴⁻被H₂还原成Au(0)，并沉积在Pt核纳米颗粒上。通过透射电子显微镜(TEM)，能量色散X射线光谱(EDS)，高分辨率TEM (HRTEM)，傅里叶变换(FFT)和X射线粉末衍射(XRD)，X射线光电子能谱(XPS)，红外光谱(IR)和H₂-程序升温还原(H₂-TPR)等表征证实了核壳结构。所制得的Pt@Au_x/Al₂O₃催化剂在常压下由固定床反应器测定其在甲苯氧化中的活性。相比于单金属催化剂Pt/Al₂O₃与Au/Al₂O₃，Pt@Au_x/Al₂O₃核壳催化剂显示出更高的催化活性，且Pt₁@Au₁/Al₂O₃对于甲苯氧化具有最好的催化活性，这归因于Au和Pt之间的电子交换促进了Au上活性氧的形成。Pt@Au_x/Al₂O₃对甲苯氧化良好的催化性能和高选择性与其较高的吸附氧物质浓度，较好的低温还原性和强相互作用有关。

关键词: 催化剂, 协同作用, 纳米材料, 核壳结构, VOCs

Abstract:

Customizing core-shell nanostructures is considered to be an efficient approach to improve the catalytic activity of metal nanoparticles. Various physiochemical and green methods have been developed for the synthesis of core-shell structures. In this study, a novel liquid-phase hydrogen reduction method was employed to form core-shell Pt@Au nanoparticles with intimate contact between the Pt and Au particles, without the use of any protective or structure-directing agents. The Pt@Au core-shell nanoparticles were prepared by depositing Au metal onto the Pt core; AuCl⁴⁻ was reduced to Au(0) by H₂ in the presence of Pt nanoparticles. The obtained Pt@Au core-shell structured nanoparticles were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), high-resolution TEM, fast Fourier transform, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and H₂-temperature programmed reduction (H₂-TPR) analyses. The EDX mapping results for the nanoparticles, as obtained from their scanning transmission electron microscopy images in the high-angle annular dark-ﬁeld mode, revealed a Pt core with Au particles grown on its surface. Fourier transform measurements were carried out on the high-resolution structure to characterize the Pt@Au nanoparticles. The lattice plane at the center of the nanoparticles corresponded to Pt, while the edge of the particles corresponded to Au. With an increase in the Au content, the intensity of the peak corresponding to Pt in the FTIR spectrum decreased slowly, indicating that the Pt nanoparticles were surrounded by Au nanoparticles, and thus confirming the core-shell structure of the nanoparticles. The XRD results showed that the peak corresponding to Pt shifted gradually toward the Au peak with an increase in the Au content, indicating that the Au particles grew on the Pt seeds; this trend was consistent with the FTIR results. Hence, it can be stated that the Pt@Au core-shell structure was successfully prepared using the liquid-phase hydrogen reduction method. The catalytic activity of the nanoparticles for the oxidation of toluene was evaluated using a fixed-bed reactor under atmospheric pressure. The XPS and H₂-TPR results showed that the Pt₁@Au₁/Al₂O₃ catalyst had the best toluene oxidation activity owing to its lowest reduction temperature, lowest Au 4d & 4f and Pt 4d & 4f binding energies, and highest Au⁰/Au^δ⁺ and Pt⁰/Pt²⁺ proportions. The Pt₁@Au₂Al₂O₃ catalyst showed high stability under dry and humid conditions. The good catalytic performance and high selectivity of Pt@Au/Al₂O₃ for toluene oxidation could be attributed to the high concentration of adsorbed oxygen species, good low-temperature reducibility, and strong interaction.

Key words: Catalyst, Synergy, Nanomaterials, Core-shell structure, VOCs

MSC2000:

O643

张超, 李思汉, 吴辰亮, 李小青, 严新焕. Pt@Au/Al₂O₃核壳纳米粒子的制备和表征及其在催化氧化甲苯中的应用[J]. 物理化学学报, 2020, 36(8): 1907057.

Chao Zhang, Sihan Li, Chenliang Wu, Xiaoqing Li, Xinhuan Yan. Preparation and Characterization of Pt@Au/Al₂O₃ Core-Shell Nanoparticles for Toluene Oxidation Reaction[J]. Acta Physico-Chimica Sinica, 2020, 36(8): 1907057.

图/表 10

Fig 1

Fig 2

Fig 3

Fig 4

Fig 5

Fig 6

Fig 7

Fig 8

Fig 9

Fig 10

参考文献 47

1	Zhang Q. ; Lee I. ; Joo J. B. ; Zaera F. ; Yin Y. Acc. Chem. Res. 2012, 46, 1816. doi: 10.1021/ar300230s
2	Sun Q. ; Zhang X. Q. ; Wang Y. ; Lu A. H. Chin. J. Catal. 2015, 36, 683. doi: 10.1016/S1872-2067(14)60298-9
3	Lee J. ; Yoo J. K. ; Kim J. ; Sohn Y. ; Rhee C. K. Electrochim. Acta 2018, 290, 244. doi: 10.1016/j.electacta.2018.09.078
4	Shim K. ; Lee W. C. ; Park M. S. ; Shahabuddin M. ; Yamauchi Y. ; Hossain M. S. A. ; Shim Y. B. ; Kim J. H. Sens. Actuator B-Chem. 2019, 278, 88. doi: 10.1016/j.snb.2018.09.048
5	Zhou S. ; McIlwrath K. ; Jackson G. ; Eichhorn B. J. Am. Chem. Soc. 2006, 128, 1780. doi: 10.1021/ja056924
6	Jiang R. ; Tung S. O. ; Tang Z. ; Li L. ; Ding L. ; Xi X. ; Liu Y. ; Zhang L. ; Zhang J. Energy Storage Mater. 2018, 12, 260. doi: 10.1016/j.ensm.2017.11.005
7	Jiang L. ; Yuan X. ; Liang J. ; Zhang J. ; Wang H. ; Zeng G. J. Power Sources 2016, 331, 408. doi: 10.1016/j.jpowsour.2016.09.054
8	Campani V. ; Giarra S. ; De Rosa G. OpenNano 2018, 3, 5. doi: 10.1016/j.onano.2017.12.001
9	Chen G. ; Wang Y. ; Xie R. ; Gong S. Adv. Drug Delivery Rev. 2018, 130, 58. doi: 10.1016/j.addr.2018.07.008
10	Zhang N. ; Liu S. ; Xu Y. Nanoscale 2012, 4, 2227. doi: 10.1039/c2nr00009a
11	Tada H. ; Suzuki F. ; Ito S. ; Akita T. ; Tanaka K. ; Kawahara T. ; Kobayashi H. J. Phys. Chem. B 2002, 106, 8714. doi: 10.1021/jp0202690
12	Yoon J. ; Baik H. ; Lee S. ; Kwon S. J. ; Lee K. Nanoscale 2014, 6, 6434. doi: 10.1039/c4nr00551a
13	Yang C. ; Zhang F. ; Lei N. ; Yang M. ; Liu F. ; Miao Z. ; Sun Y. ; Zhao X. ; Wang A. Chin. J. Catal. 2018, 39, 1366. doi: 10.1016/s1872-2067(18)63103-1
14	Zhang Y. ; Liu Y. ; Xie S. ; Huang H. ; Guo G. ; Dai H. ; Deng J. Environ. Int. 2019, 128, 335. doi: 10.1016/j.envint.2019.04.062
15	Qi Y. ; Shen L. ; Zhang J. ; Yao J. ; Lu R. ; Miyakoshi T. Environ. Pollut. 2019, 245, 810. doi: 10.1016/j.envpol.2018.11.057
16	Morin J. ; Gandolfo A. ; Temime-Roussel B. ; Strekowski R. ; Brochard G. ; Bergé. V% Gligorovski S. ; Wortham H. Build. Environ. 2019, 156, 225. doi: 10.1016/j.buildenv.2019.04.031
17	Song M. ; Liu X. ; Zhang Y. ; Shao M. ; Lu K. ; Tan Q. ; Feng M. ; Qu Y. Atmos. Environ. 2019, 201, 28. doi: 10.1016/j.atmosenv.2018.12.019
18	Kim K. ; Boo S. ; Ahn H. J. Ind. Eng. Chem. 2009, 15, 92. doi: 10.1016/j.jiec.2008.09.005
19	Zhu A. ; Zhou Y. ; Wang Y. ; Zhu Q. ; Liu H. ; Zhang Z. ; Lu H. J. Rare Earths 2018, 36, 1272. doi: 10.1016/j.jre.2018.03.032
20	Feng Z. ; Ma Y. ; Natarajan V. ; Zhao Q. ; Ma X. ; Zhan J. Sens. Actuator B-Chem. 2018, 255, 884. doi: 10.1016/j.snb.2017.08.138
21	Gaálová J. ; Topka P. ; Kaluža L. ; Soukup K. ; Barbier J. Catal. Today. 2019, 333, 190. doi: 10.1016/j.cattod.2018.04.005
22	Vallejos S. ; Gràcia I. ; Bravo J. ; Figueras E. ; Hubálek J. ; Cané C. Talanta 2015, 139, 27. doi: 10.1016/j.talanta.2015.02.034
23	Usón L. ; Colmenares M. G. ; Hueso J. L. ; Sebastián V. ; Balas F. ; Arruebo M. ; Santamaría J. Catal. Today 2014, 227, 179. doi: 10.1016/j.cattod.2013.08.014
24	Mori M. ; Nishimura H. ; Itagaki Y. ; Sadaoka Y. ; Traversa E. Sens. Actuator B-Chem. 2009, 143, 56. doi: 10.1016/j.snb.2009.09.001
25	Li J. H. ; Ao P. ; Li X. Q. ; Xu X. S. ; Xu X. X. ; Gao X. ; Yan X. H. Acta Phys. -Chim. Sin. 2015, 31, 173. doi: 10.3866/PKU.WHXB201411131
	李加衡; 敖平; 李小青; 许响生; 徐潇潇; 高翔; 严新焕. 物理化学学报, 2015, 31, 173. doi: 10.3866/PKU.WHXB201411131
26	Sun S. ; Wang Y. ; Wang L. N. ; Guo T. ; Yuan X. ; Zhang D. ; Xue Z. ; Zhou X. ; Lu X. J. Alloy. Compd. 2019, 793, 635. doi: 10.1016/j.jallcom.2019.04.212
27	Peng C. ; Pan N. ; Qian Z. ; Wei X. ; Shao G. Talanta 2017, 175, 114. doi: 10.1016/j.talanta.2017.06.005
28	Takahashi S. ; Todoroki N. ; Myochi R. ; Nagao T. ; Taguchi N. ; Ioroi T. ; Feiten F. E. ; Wakisaka Y. ; Asakura K. ; Sekizawa O. ; et al J. Electroanal. Chem. 2019, 842, 1. doi: 10.1016/j.jelechem.2019.04.053
29	Lewis L. N. ; Krafft T. A. ; Huffman J. C. Inorg. Chem. 1992, 31, 3555. doi: 10.1021/ic00043a014
30	Kristian N. ; Wang X. Electrochem. Commun. 2008, 10, 12. doi: 10.1016/j.elecom.2007.10.011
31	Grzelczak M. ; Pérez-Juste J. ; Rodríguez-González B. ; Liz-Marzán L. M. J. Mater. Chem. 2006, 16, 3946. doi: 10.1039/b606887a
32	Liao M. ; Li W. ; Xi X. ; Luo C. ; Gui S. ; Jiang C. ; Mai Z. ; Chen B. H. J. Electroanal. Chem. 2017, 791, 124. doi: 10.1016/j.jelechem.2017.03.024
33	Cao R. ; Xia T. ; Zhu R. ; Liu Z. ; Guo J. ; Chang G. ; Zhang Z. ; Liu X. ; He Y. Appl. Surf. Sci. 2018, 433, 840. doi: 10.1016/j.apsusc.2017.10.104
34	Nishita M. ; Park S. Y. ; Nishio T. ; Kamizaki K. ; Wang Z. ; Tamada K. ; Takumi T. ; Hashimoto R. ; Otani H. ; Pazour G. J. ; et al Sci. Rep. 2017, 7, 1306. doi: 10.1038/s41598-016-0028-x
35	Guo S. ; Li J. ; Dong S. ; Wang E. J. Phys. Chem. C 2010, 114, 15337. doi: 10.1021/jp104942d
36	Yang H. ; Deng J. ; Liu Y. ; Xie S. ; Wu Z. ; Dai H. J. Mol. Catal. A-Chem. 2016, 414, 9. doi: 10.1016/j.molcata.2015.12.010
37	Pei W. ; Liu Y. ; Deng J. ; Zhang K. ; Hou Z. ; Zhao X. ; Dai H. Appl. Catal. B-Environ. 2019, 256, 117814. doi: 10.1016/j.apcatb.2019.117814
38	He G. ; Song Y. ; Liu K. ; Walter A. ; Chen S. ; Chen S. ACS Catal. 2013, 3, 831. doi: 10.1021/cs400114s
39	Zhang X. ; Li Z. ; Zhao J. ; Cui Y. ; Tan B. ; Wang J. ; Zhang C. ; He G. Korean J. Chem. Eng. 2017, 34, 1. doi: 10.1007/s11814-017-0092-3
40	Lefèvre G. ; Duc M. ; Lepeut P. ; Caplain R. ; Fédoroff M. Langmuir 2002, 18, 7530. doi: 10.1021/la025651i
41	Meng T. ; Wang L. ; Jia H. ; Gong T. ; Feng Y. ; Li R. ; Wang H. ; Zhang Y. J. Colloid Interface Sci. 2019, 536, 424. doi: 10.1016/j.jcis.2018.10.076
42	Cao Z. ; Bu J. ; Zhong Z. ; Sun C. ; Zhang Q. ; Wang J. ; Chen S. ; Xie X. Appl. Catal. A-Gen. 2019, 578, 105. doi: 10.1016/j.apcata.2019.04.006
43	Chenakin S. ; Kruse N. J. Catal. 2018, 358, 224. doi: 10.1016/j.jcat.2017.12.010
44	Figueiredo N. M. ; Carvalho N. J. M. ; Cavaleiro A. Appl. Surf. Sci. 2011, 257, 5793. doi: 10.1016/j.apsusc.2011.01.104
45	Nartova A. V. ; Gharachorlou A. ; Bukhtiyarov A. V. ; Kvon R. I. ; Bukhtiyarov V. I. Appl. Surf. Sci. 2017, 401, 341. doi: 10.1016/j.apsusc.2016.12.179
46	Smirnov M. Y. ; Kalinkin A. V. ; Vovk E. I. ; Simonov P. A. ; Gerasimov E. Y. ; Sorokin A. M. ; Bukhtiyarov V. I. Appl. Surf. Sci. 2018, 428, 972. doi: 10.1016/j.apsusc.2017.09.205
47	Ousmane M. ; Liotta L. F. ; Carlo G. D. ; Pantaleo G. ; Venezia A. M. ; Deganello G. ; Retailleau L. ; Boreave A. ; Giroir-Fendler A. Appl. Catal. B-Environ. 2011, 101, 629. doi: 10.1016/j.apcatb.2010.11.004

[1]	周雪梅. 二氧化钛负载单原子催化剂用于光催化反应的研究[J]. 物理化学学报, 2021, 37(6): 2008064 -0 .
[2]	王艳秋, 钟子欣, 刘唐康, 刘国亮, 洪昕林. Cu@UiO-66衍生的Cu⁺-ZrO₂界面位点用于高效催化CO₂加氢制甲醇[J]. 物理化学学报, 2021, 37(5): 2007089 -0 .
[3]	孟怡辰, 况思宇, 刘海, 范群, 马新宾, 张生. 面向CO₂电化学转化的铜基催化剂研究进展[J]. 物理化学学报, 2021, 37(5): 2006034 -0 .
[4]	吴进, 刘京, 夏雾, 任颖异, 王锋. 基于CdS和CdSe纳米半导体材料的可见光催化二氧化碳还原研究进展[J]. 物理化学学报, 2021, 37(5): 2008043 -0 .
[5]	李聪明, 陈阔, 王晓月, 薛楠, 杨恒权. 探究Cu/ZnO相互作用对CO₂加氢制甲醇反应性能的影响[J]. 物理化学学报, 2021, 37(5): 2009101 -0 .
[6]	李琳, 沈水云, 魏光华, 章俊良. 基于血红素衍生的中空非贵金属催化剂氧还原反应电催化活性[J]. 物理化学学报, 2021, 37(3): 1911011 -0 .
[7]	周远, 韩娜, 李彦光. 钯基纳米材料电化学还原二氧化碳研究进展[J]. 物理化学学报, 2020, 36(9): 2001041 -0 .
[8]	王艺蒙, 张申平, 葛宇, 王臣辉, 胡军, 刘洪来. 多孔双金属氧化物/碳复合光催化剂对四环素的高效光催化降解[J]. 物理化学学报, 2020, 36(8): 1905083 -0 .
[9]	刘丹叶,陈东,刘卉,杨军. 贵金属在Ag₂S纳米颗粒中由内向外的迁移现象[J]. 物理化学学报, 2020, 36(7): 1906069 -0 .
[10]	刘冬梅,陈秀梅,袁泽,闾敏,殷丽莎,谢小吉,黄岭. 上转换纳米粒子的Y(OH)CO₃壳层包覆及壳层转化[J]. 物理化学学报, 2020, 36(7): 1907011 -0 .
[11]	方波,冯立纲. 纳米颗粒结合ZIF-67衍生的PtCo-NC催化剂用于醇类燃料电氧化[J]. 物理化学学报, 2020, 36(7): 1905023 -0 .
[12]	王梁,朱澄鹭,殷丽莎,黄维. Pt-M (M = Co, Ni, Fe)/g-C₃N₄复合材料构建及其高效光解水制氢性能[J]. 物理化学学报, 2020, 36(7): 1907001 -0 .
[13]	苗静,郭睿凤,刘志宏. BaO∙4B₂O₃∙5H₂O纳米材料的制备及其对聚丙烯阻燃性能的热分解动力学方法评价[J]. 物理化学学报, 2020, 36(6): 1905052 -0 .
[14]	孙万军,林军奇,梁向明,杨峻懿,马宝春,丁勇. 基于立方烷结构的分子催化剂在光催化水氧化中的研究进展[J]. 物理化学学报, 2020, 36(3): 1905025 -0 .
[15]	张若兰,王超,陈浩,赵恒,刘婧,李昱,苏宝连. 硫化镉反蛋白石光子晶体制备及光解水制氢[J]. 物理化学学报, 2020, 36(3): 1803014 -0 .

Pt@Au/Al₂O₃核壳纳米粒子的制备和表征及其在催化氧化甲苯中的应用

Preparation and Characterization of Pt@Au/Al₂O₃ Core-Shell Nanoparticles for Toluene Oxidation Reaction

RichHTML

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 47

相关文章 15

Metrics

本文评价

推荐阅读 0