氧化铈形貌对Pd纳米粒子分散的影响

doi:10.1016/S1872-2067(20)63725-1

催化学报 ›› 2021, Vol. 42 ›› Issue (12): 2234-2241.DOI: 10.1016/S1872-2067(20)63725-1

氧化铈形貌对Pd纳米粒子分散的影响

董春燕^a^,^b, 周燕^a^,^*(), 塔娜^a, 刘雯璐^a, 李名润^a, 申文杰^a^,^#()

^a中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连116023
^b中国科学院大学, 北京100049

收稿日期:2020-12-06 接受日期:2020-12-06 出版日期:2021-12-18 发布日期:2020-12-10
通讯作者: 周燕,申文杰
基金资助:
国家自然科学基金(21533009);国家自然科学基金(21761132031)

Shape impact of nanostructured ceria on the dispersion of Pd species

Chunyan Dong^a^,^b, Yan Zhou^a^,^*(), Na Ta^a, Wenlu Liu^a, Mingrun Li^a, Wenjie Shen^a^,^#()

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2020-12-06 Accepted:2020-12-06 Online:2021-12-18 Published:2020-12-10
Contact: Yan Zhou,Wenjie Shen
About author:# E-mail: shen98@dicp.ac.cn
* E-mail: zhouyan@dicp.ac.cn;
Supported by:
National Natural Science Foundation of China(21533009);National Natural Science Foundation of China(21761132031)

摘要/Abstract

摘要：

氧化铈由于在氧化和还原气氛下具有快速Ce⁴⁺/Ce³⁺氧化还原循环作用, 使其具有优异的储放氧能力, 不仅可以分散和稳定金属粒子, 还可在界面处与金属物种发生化学键合, 并形成活性位点, 因此已被广泛应用于多个催化反应体系, 且表现出显著的形貌效应. 通过对氧化铈形貌进行调控, 使其暴露特定(111)、(110)和(100)晶面, 已成为调节金属-氧化铈相互作用强度及金属物种电子、几何结构, 提高催化性能的有效策略, 但对其机制及活性位结构还没有清晰的认识.

我们以氧化铈纳米粒子和纳米立方体为载体, 其中氧化铈立方体平均尺寸为23 nm, 主要暴露6个{100}晶面, 边缘和截角暴露少量{110}及{111}晶面; 球形氧化铈纳米粒子平均尺寸为11 nm, 主要暴露{111}晶面; 并进一步将2.0 wt% Pd物种分散在氧化铈立方体和球形纳米粒子上, 通过扫描透射电子显微镜(STEM)和X射线光电子能谱(XPS)等研究了钯物种在氧化铈球形粒子和立方体上的原子结构和化学环境, 进而分析了纳米结构氧化铈形貌对钯物种分散的影响. 在球形氧化铈纳米粒子上主要形成了平均尺寸为2.0 nm的非晶态Pd纳米粒子以及极小的Pd物种, 这主要是因为球形氧化铈纳米粒子上丰富的表面氧空位可通过Pd-CeO₂强相互作用和Pd物种紧密键合. 氧化铈立方体上的晶态Pd粒子尺寸为2.9 nm, 金属与载体之间具有明显的界面, 且Pd原子嵌入到氧化铈晶格中. 同时, CO化学吸附测试也证明了氧化铈球形粒子上的钯分散度(70%)高于氧化铈立方体(52%). 对于甲烷燃烧反应, 主要涉及发生在金属粒子表面的PdO/Pd氧化还原循环, 即Pd被O₂氧化, PdO被CH₄还原, 富氧条件下决速步骤是PdO对CH₄中C-H的活化, 因此氧化铈立方体表面大尺寸的晶态Pd粒子被氧化后更容易被CH₄还原, 有利于PdO/Pd氧化还原循环, 从而具有更高的活性和稳定性; 然而在CO氧化反应中Pd/CeO₂却呈现了相反的形貌效应, 这是由于该反应遵循Mars-van Krevelen机理: CO吸附在金属Pd上, 化学吸附的CO移动到钯-氧化铈界面, 被氧化铈晶格氧氧化成CO₂, 产生的氧空位被表面氧补充, 最后表面氧空位被气相氧补充; 由于氧化铈球形粒子上的较小尺寸Pd具有更大的钯-氧化铈界面周长和更强的氧物种移动性, 更易完成界面处的氧化还原循环, 因此具有更高的CO氧化活性.

关键词: Pd/CeO₂, Pd粒子, 氧化铈形貌, 金属-载体界面, 甲烷燃烧, CO氧化

Abstract:

The shape impact of nanostructured ceria on the dispersion of Pd species was investigated by analyzing the atomic configuration and the bonding environment of Pd species over spherical and cubic ceria particles, using STEM and XPS. Amorphous Pd particles of about 2.0 nm, with a substantial amount of tiny Pd species, dispersed on spherical ceria, primarily due to the enriched surface oxygen vacancies that bonded the Pd species tightly. While faceted Pd particles of about 2.9 nm located on cubic ceria with distinct interfaces where Pd atoms embedded into the ceria lattice. The crystalline Pd particles on ceria cubes were highly active and stable for methane combustion that occurred on the metal surface via a facile PdO/Pd redox cycle; while the amorphous Pd particles on spherical ceria particles were featured by a significantly higher activity and stability towards CO oxidation, where the Pd-ceria interface served as the active sites.

Key words: Pd/CeO₂, Pd particle, Ceria shape, Metal-support interface, Methane combustion, CO oxidation

董春燕, 周燕, 塔娜, 刘雯璐, 李名润, 申文杰. 氧化铈形貌对Pd纳米粒子分散的影响[J]. 催化学报, 2021, 42(12): 2234-2241.

Chunyan Dong, Yan Zhou, Na Ta, Wenlu Liu, Mingrun Li, Wenjie Shen. Shape impact of nanostructured ceria on the dispersion of Pd species[J]. Chinese Journal of Catalysis, 2021, 42(12): 2234-2241.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63725-1

https://www.cjcatal.com/CN/Y2021/V42/I12/2234

图/表 8

Fig. 1. STEM images of the Pd-P catalyst.

Fig. 2. STEM images of the Pd-C catalyst (a-c) and the enlarged image (d) and a geometrical structure model (e) of the square area shown in (c).

Fig. 3. XPS spectra of Pd 3d (a), Ce 3d (b) and O 1s (c) in the Pd/CeO2 catalysts.

Fig. 4. CH4 conversion over the Pd/CeO2 catalysts during the heating and cooling cycles. Reaction conditions: 1.0 vol% CH4/20.0 vol% O2/He, 72000 gcat-1 h-1.

Fig. 5. Methane combustion over the Pd/CeO2 catalysts at 330 °C. Reaction conditions: 1.0 vol% CH4/20.0 vol% O2/He, 72000 mL gcat-1 h-1.

Fig. 6. XPS of Pd 3d (a), Ce 3d (b) and O 1s (c) in the spent Pd/CeO2 catalysts after methane combustion.

Fig. 7. STEM images of the spent Pd-C (a) and Pd-P (b) catalyst after CH4 combustion.

Fig. 8. CO oxidation over the Pd/CeO2 catalysts at 110 °C. Reaction conditions: 1.0 vol% CO/0.5 vol% O2/He, 144000 mL g cat-1 h-1.

参考文献

[1]	M. Cargnello, V. V. T Doan-Nguyen, T. R. Gordon, R. E. Diaz, E. A. Stach, R. J. Gorte, P. Fornasiero, C. B. Murray, Science, 2013, 341, 771-773.
[2]	T. Montini, M. Melchionna, M. Monai, P. Fornasiero, Chem. Rev., 2016, 116, 5987-6041.
[3]	A. Trovarelli, J. Llorca, ACS Catal., 2017, 7, 4716-4735.
[4]	S. Chang, M. Li, Q. Hua, L. Zhang, Y. Ma, B. Ye, W. Huang, J. Catal., 2012, 293, 195-204.
[5]	N. Ta, J. J. Liu, S. Chenna, P. A. Crozier, Y. Li, A. Chen, W. Shen, J. Am. Chem. Soc., 2012, 134, 20585-20588.
[6]	Y. Lin, Z. Wu, J. Wen, K. Ding, X. Yang, K. R. Poeppelmeier, L. D. Marks, Nano Lett., 2015, 15, 5375-5381.
[7]	Y. Zhou, Y. Li, W. Shen, Chem. Asian J., 2016, 11, 1470-1488.
[8]	S. Zhang, Z. Xia, T. Ni, Z. Zhang, Y. Ma, Y. Qu, J. Catal., 2018, 359, 101-111.
[9]	J. Li, Z. Liu, D. A. Cullen, W. Hu, J. Huang, L. Yao, Z. Peng, P. Liao, R. Wang, ACS Catal., 2019, 9, 11088-11103.
[10]	S. Colussi, A. Gayen, M. Farnesi Camellone, M. Boaro, J. Llorca, S. Fabris, A. Trovarelli, Angew. Chem. Int. Ed., 2009, 48, 8481-8484.
[11]	M. Cargnello, J. J. D Jaen, J. C. H. Garrido, K. Bakhmutsky, T. Montini, J. J. Calvino Gamez, R. J. Gorte, P. Fornasiero, Science, 2012, 337, 713-717.
[12]	T. Guo, J. Du, J. Li, J. Mater. Sci., 2016, 51, 10917-10925.
[13]	K. Murata, Y. Mahara, J. Ohyama, Y. Yamamoto, S. Arai, A. Satsuma, Angew. Chem. Int. Ed., 2017, 56, 15993-15997.
[14]	Y. Lei, W. Li, Q. Liu, Q. Lin, X. Zheng, Q. Huang, S. Guan, X. Wang, C. Wang, F. Li, Fuel, 2018, 233, 10-20.
[15]	M. Danielis, S. Colussi, C. de Leitenburg, L. Soler, J. Llorca, A. Trovarelli, Angew. Chem. Int. Ed., 2018, 57, 10212-10216.
[16]	H. Peng, C. Rao, N. Zhang, X. Wang, W. Liu, W. Mao, L. Han, P. Zhang, S. Dai, Angew. Chem. Int. Ed., 2018, 57, 8953-8957.
[17]	K. Murata, D. Kosuge, J. Ohyama, Y. Mahara, Y. Yamamoto, S. Arai, A. Satsuma, ACS Catal., 2020, 10, 1381-1387.
[18]	S. Colussi, P. Fornasiero, A. Trovarelli, Chin. J. Catal., 2020, 41, 938-950.
[19]	Z. Hu, X. Liu, D. Meng, Y. Guo, Y. Guo, G. Lu, ACS Catal., 2016, 6, 2265-2279.
[20]	J. Wu, L. Zeng, D. Cheng, F. Chen, X. Zhan, J. Gong, Chin. J. Catal., 2016, 37, 83-90.
[21]	G. Spezzati, A. D. Benavidez, A. T DeLaRiva, Y. Su, J. P. Hofmann, S. Asahina, E. J. Olivier, J. H. Neethling, J. T. Miller, A. K. Datye, E. J. M. Hensen, Appl. Catal. B, 2019, 243, 36-46.
[22]	F. Wang, C. Li, X. Zhang, M. Wei, D. G. Evans, X. Duan, J. Catal., 2015, 329, 177-186.
[23]	C. Dong, Y. Zhou, N. Ta, W. Shen, CrystEngComm, 2020, 22, 3033-3041.
[24]	R. V. Gulyaev, T. Y. Kardash, S. E. Malykhin, O. A. Stonkus, A. S. Ivanova, A. I. Boronin, Phys. Chem. Chem. Phys., 2014, 16, 13523-13539.
[25]	K. R. Priolkar, P. Bera, P. R. Sarode, M. S. Hegde, S. Emura, R. Kumashiro, N. P. Lalla, Chem. Mater., 2002, 14, 2120-2128.
[26]	S. Hinokuma, Hi. Fujii, Ma. Okamoto, K. Ikeue, M. Machida, Chem. Mater., 2010, 22, 6183-6190.
[27]	Y.-Q. Su, I. A. W. Filot, J.-X. Liu, E. J. M. Hensen, ACS Catal., 2018, 8, 75-80.
[28]	M. S. Hegde, P. Bera, Catal. Today, 2015, 253, 40-50.
[29]	O. A. Stonkus, T. Y. Kardash, E. M. Slavinskaya, V. I. Zaikovskii, A. I. Boronin, ChemCatChem, 2019, 11, 3505-3521.
[30]	Z. Wang, Z. Huang, J. T. Brosnahan, S. Zhang, Y. Guo, Y. Guo, L. Wang, Y. Wang, W. Zhan, Environ. Sci. Technol., 2019, 53, 5349-5358.
[31]	S. Li, Y. Zhang, J. Shi, G. Zhu, Y. Xie, Z. Li, R. Wang, H. Zhu, Nanomaterials, 2020, 10, 31.
[32]	H. X. Mai, L. D. Sun, Y. W. Zhang, R. Si, W. Feng, H. P. Zhang, H. C. Liu, C. H. Yan, J. Phys. Chem. B, 2005, 109, 24380-24385.
[33]	J. Chen, Y. Wu, W. Hu, P. Qu, G. Zhang, P. Granger, L. Zhong, Y. Chen, Appl. Catal. B, 2020, 264, 118475.
[34]	A. Hellman, A. Resta, N. M. Martin, J. Gustafson, A. Trinchero, P. A. Carlsson, O. Balmes, R. Felici, R. van Rijn, J. W. Frenken, J. N. Andersen, E. Lundgren, H. Gronbeck, J. Phys. Chem. Lett., 2012, 3, 678-682.
[35]	J. B. Miller, M. Malatpure, Appl. Catal. A, 2015, 495, 54-62.
[36]	Y. H. Chin, M. García-Diéguez, E. Iglesia, J. Phys. Chem. C, 2016, 120, 1446-1460.
[37]	E. D. Goodman, A. C Johnston-Peck, E. M. Dietze, C. J. Wrasman, A. S. Hoffman, F. Abild-Pedersen, S. R. Bare, P. N. Plessow, M. Cargnello, Nat. Catal., 2019, 2, 748-755.
[38]	K. Tang, Y. Ren, W. Liu, J. Wei, J. Guo, S. Wang, Y. Yang, ACS Appl. Mater. Interfaces, 2018, 10, 13614-13624.
[39]	H. J. Kim, M. G. Jang, D. Shin, J. W. Han, ChemCatChem, 2019, 12, 11-26.

氧化铈形貌对Pd纳米粒子分散的影响

Shape impact of nanostructured ceria on the dispersion of Pd species

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 8

参考文献

相关文章 15

编辑推荐

Metrics

[1]	翁雪霏, 杨双莉, 丁丁, 陈明树, 万惠霖. 宽波段原位红外吸收光谱在Pd/SiO₂和Cu/SiO₂催化剂上CO氧化中的应用[J]. 催化学报, 2022, 43(8): 2001-2009.
[2]	欧阳, 李松达, 王飞, 段心怡, 袁文涛, 杨杭生, 张泽, 王勇. 二氧化钛负载的铂纳米颗粒在CO和O₂环境下表面平台位点和台阶位点的可逆转变[J]. 催化学报, 2022, 43(8): 2026-2033.
[3]	朱纯, 梁锦霞, 王阳刚, 李隽. MXene负载的非贵金属单原子催化剂催化CO氧化反应[J]. 催化学报, 2022, 43(7): 1830-1841.
[4]	高明洋, 龚忠苗, 翁雪霏, 尚炜翔, 柴玉超, 戴卫理, 武光军, 关乃佳, 李兰冬. MFI分子筛限域空间内Pd催化剂上甲烷燃烧[J]. 催化学报, 2021, 42(10): 1689-1699.
[5]	郑珠媛, 王栋, 张毅, 杨帆, 龚学庆. CeO₂/Pt(111)反向催化剂结构和活性的密度泛函理论研究[J]. 催化学报, 2020, 41(9): 1360-1368.
[6]	胡文德, 邵正将, 曹宵鸣, 胡培君. Co₃O₄(110)表面甲烷催化燃烧中的单位点和多位点性能对比:第一性原理动力学蒙特卡洛研究[J]. 催化学报, 2020, 41(9): 1369-1377.
[7]	周燕, 陈阿玲, 宁静, 申文杰. 铜-氧化铈界面:几何及电子结构[J]. 催化学报, 2020, 41(6): 928-937.
[8]	Linxi Wang, Shyam Deo, Kerry Dooley, Michael J. Janik, Robert M. Rioux. 金属核及氧化铈的物理化学性质对一氧化碳氧化的影响[J]. 催化学报, 2020, 41(6): 951-962.
[9]	高玉仙, 张振华, 李兆瑞, 黄伟新. 从头开始理解形貌依赖的CuO_x-CeO₂相互作用[J]. 催化学报, 2020, 41(6): 1006-1016.
[10]	盛丽萍, 马朝霞, 陈思园, 楼锦泽, 李成业, 李松达, 张泽, 王勇, 杨杭生. 无氧条件下Pd/CeO₂催化剂表面NH₃还原NO过程中N₂O形成机理研究[J]. 催化学报, 2019, 40(7): 1070-1077.
[11]	邵斌, 赵雯宁, 苗樹, 黄家辉, 王丽丽, 李杲, 申文杰. 二氧化钛负载金催化剂:界面效应[J]. 催化学报, 2019, 40(10): 1534-1539.
[12]	张泽树, 李经纬, 易婷, 孙立伟, 张一波, 胡学风, 崔文浩, 杨向光. 调控尖晶石Co³⁺和Ni³⁺表面密度来提高催化甲烷氧化活性[J]. 催化学报, 2018, 39(7): 1228-1239.
[13]	王成雄, 夏文正, 赵云昆. Rh-CeO₂催化剂表面CO还原NO反应中羟基介导NH₃生成问题的探讨[J]. 催化学报, 2017, 38(8): 1399-1405.
[14]	赵振阳, 王博伟, 马健, 詹望成, 王丽, 郭杨龙, 郭耘, 卢冠忠. 负载型Pd/SnO₂催化剂低温催化甲烷燃烧[J]. 催化学报, 2017, 38(8): 1322-1329.
[15]	徐红, 倪可, 李小昆, 朱胜, 范果红. 酸洗Pt-Fe和Pt-Co催化剂在CO氧化反应中的对比研究[J]. 催化学报, 2017, 38(7): 1261-1269.