Preparation and Characterization of Pt@Au/Al<sub>2</sub>O<sub>3</sub> Core-Shell Nanoparticles for Toluene Oxidation Reaction

Citation: Zhang Chao, Li Sihan, Wu Chenliang, Li Xiaoqing, Yan Xinhuan. Preparation and Characterization of Pt@Au/Al₂O₃ Core-Shell Nanoparticles for Toluene Oxidation Reaction[J]. Acta Physico-Chimica Sinica, 2020, 36(8): 1907057-0. doi: 10.3866/PKU.WHXB201907057 shu

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

.
浙江工业大学绿色化学合成技术国家重点实验室培育基地，杭州 310014

通讯作者: 严新焕, xhyan@zjut.edu.cn

基金项目:
国家重点研发计划(2017YFC0210900)与浙江省科技计划项目(2016C31104)资助

国家重点研发计划 2017YFC0210900

浙江省科技计划项目 2016C31104

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:

English

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

State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, P. R. China

Corresponding author: Yan Xinhuan, xhyan@zjut.edu.cn

Received Date: 19 July 2019
Accepted Date: 09 September 2019
Revised Date: 27 August 2019
Available Online: 15 August 2020
Fund Project:
The project was supported by the National Key R&D Program (2017YFC0210900) and Zhejiang Science and Technology Plan Project, China (2016C31104)

the National Key R&D Program 2017YFC0210900

Zhejiang Science and Technology Plan Project, China 2016C31104

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:

1. [1]
  Zhang, Q.; Lee, I.; Joo, J. B.; Zaera, F.; Yin, Y. Acc. Chem. Res. 2012, 46, 1816. doi: 10.1021/ar300230s doi: 10.1021/ar300230s
2. [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 doi: 10.1016/S1872-2067(14)60298-9
3. [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 doi: 10.1016/j.electacta.2018.09.078
4. [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 doi: 10.1016/j.snb.2018.09.048
5. [5]
  Zhou, S.; McIlwrath, K.; Jackson, G.; Eichhorn, B. J. Am. Chem. Soc. 2006, 128, 1780. doi: 10.1021/ja056924 doi: 10.1021/ja056924
6. [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 doi: 10.1016/j.ensm.2017.11.005
7. [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 doi: 10.1016/j.jpowsour.2016.09.054
8. [8]
  Campani, V.; Giarra, S.; De Rosa, G. OpenNano 2018, 3, 5. doi: 10.1016/j.onano.2017.12.001 doi: 10.1016/j.onano.2017.12.001
9. [9]
  Chen, G.; Wang, Y.; Xie, R.; Gong, S. Adv. Drug Delivery Rev. 2018, 130, 58. doi: 10.1016/j.addr.2018.07.008 doi: 10.1016/j.addr.2018.07.008
10. [10]
  Zhang, N.; Liu, S.; Xu, Y. Nanoscale 2012, 4, 2227. doi: 10.1039/c2nr00009a doi: 10.1039/c2nr00009a
11. [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 doi: 10.1021/jp0202690
12. [12]
  Yoon, J.; Baik, H.; Lee, S.; Kwon, S. J.; Lee, K. Nanoscale 2014, 6, 6434. doi: 10.1039/c4nr00551a doi: 10.1039/c4nr00551a
13. [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 doi: 10.1016/s1872-2067(18)63103-1
14. [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 doi: 10.1016/j.envint.2019.04.062
15. [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 doi: 10.1016/j.envpol.2018.11.057
16. [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 doi: 10.1016/j.buildenv.2019.04.031
17. [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 doi: 10.1016/j.atmosenv.2018.12.019
18. [18]
  Kim, K.; Boo, S.; Ahn, H. J. Ind. Eng. Chem. 2009, 15, 92. doi: 10.1016/j.jiec.2008.09.005 doi: 10.1016/j.jiec.2008.09.005
19. [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 doi: 10.1016/j.jre.2018.03.032
20. [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 doi: 10.1016/j.snb.2017.08.138
21. [21]
  Gaálová, J.; Topka, P.; Kaluža, L.; Soukup, K.; Barbier, J. Catal. Today. 2019, 333, 190. doi: 10.1016/j.cattod.2018.04.005 doi: 10.1016/j.cattod.2018.04.005
22. [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 doi: 10.1016/j.talanta.2015.02.034
23. [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 doi: 10.1016/j.cattod.2013.08.014
24. [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 doi: 10.1016/j.snb.2009.09.001
25. [25]
  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.WHXB201411131Li, 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
26. [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 doi: 10.1016/j.jallcom.2019.04.212
27. [27]
  Peng, C.; Pan, N.; Qian, Z.; Wei, X.; Shao, G. Talanta 2017, 175, 114. doi: 10.1016/j.talanta.2017.06.005 doi: 10.1016/j.talanta.2017.06.005
28. [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 doi: 10.1016/j.jelechem.2019.04.053
29. [29]
  Lewis, L. N.; Krafft, T. A.; Huffman, J. C. Inorg. Chem. 1992, 31, 3555. doi: 10.1021/ic00043a014 doi: 10.1021/ic00043a014
30. [30]
  Kristian, N.; Wang, X. Electrochem. Commun. 2008, 10, 12. doi: 10.1016/j.elecom.2007.10.011 doi: 10.1016/j.elecom.2007.10.011
31. [31]
  Grzelczak, M.; Pérez-Juste, J.; Rodríguez-González, B.; Liz-Marzán, L. M. J. Mater. Chem. 2006, 16, 3946. doi: 10.1039/b606887a doi: 10.1039/b606887a
32. [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 doi: 10.1016/j.jelechem.2017.03.024
33. [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 doi: 10.1016/j.apsusc.2017.10.104
34. [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 doi: 10.1038/s41598-016-0028-x
35. [35]
  Guo, S.; Li, J.; Dong, S.; Wang, E. J. Phys. Chem. C 2010, 114, 15337. doi: 10.1021/jp104942d doi: 10.1021/jp104942d
36. [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 doi: 10.1016/j.molcata.2015.12.010
37. [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 doi: 10.1016/j.apcatb.2019.117814
38. [38]
  He, G.; Song, Y.; Liu, K.; Walter, A.; Chen, S.; Chen, S. ACS Catal. 2013, 3, 831. doi: 10.1021/cs400114s doi: 10.1021/cs400114s
39. [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 doi: 10.1007/s11814-017-0092-3
40. [40]
  Lefèvre, G.; Duc, M.; Lepeut, P.; Caplain, R.; Fédoroff, M. Langmuir 2002, 18, 7530. doi: 10.1021/la025651i doi: 10.1021/la025651i
41. [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 doi: 10.1016/j.jcis.2018.10.076
42. [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 doi: 10.1016/j.apcata.2019.04.006
43. [43]
  Chenakin, S.; Kruse, N. J. Catal. 2018, 358, 224. doi: 10.1016/j.jcat.2017.12.010 doi: 10.1016/j.jcat.2017.12.010
44. [44]
  Figueiredo, N. M.; Carvalho, N. J. M.; Cavaleiro, A. Appl. Surf. Sci. 2011, 257, 5793. doi: 10.1016/j.apsusc.2011.01.104 doi: 10.1016/j.apsusc.2011.01.104
45. [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 doi: 10.1016/j.apsusc.2016.12.179
46. [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 doi: 10.1016/j.apsusc.2017.09.205
47. [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 doi: 10.1016/j.apcatb.2010.11.004

扫一扫看文章

计量

PDF下载量: 0
文章访问数: 19
HTML全文浏览量: 0

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

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

通讯作者: 严新焕, xhyan@zjut.edu.cn

English

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

Corresponding author: Yan Xinhuan, xhyan@zjut.edu.cn

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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