稀土铈基催化材料氧空位的表征方法综述

doi:10.11949/0438-1157.20200131

摘要/Abstract

摘要：

氧空位（oxygen vacancy, Ov）是金属氧化物缺陷的一种，在多相催化、储能材料、能源化工等众多领域都发挥着重要的作用，因而关于其在理论和实验方面的研究都得到了广泛关注。以稀土CeO₂这一广泛应用于能源、环境等领域的催化材料为例，简单归纳了一些氧空位检测的常用表征方法，包括拉曼(Raman)、电子顺磁共振(EPR)、正电子湮没能谱(PALS)、固体核磁(ss-NMR)、X射线光电子能谱(XPS)和扫描隧道显微镜(STM)等，同时对各种表征方法的结果分析进行了举例说明。在此基础上，对氧空位表征技术未来的发展方向提出了一些看法。希望可以对稀土铈基催化材料缺陷相关的表征及研究提供支持。

关键词: 氧空位, 表征技术, 催化剂, CeO₂, 纳米结构, 表面

Abstract:

Oxygen vacancy (Ov) is a kind of metal oxide defect, and plays an important role in many fields such as heterogeneous catalysis, energy storage materials, energy and chemical industry, its research on theory and experiment has received extensive attention. We take the rare earth CeO₂, a catalytic material widely used in energy, environment and other fields as an example, and briefly summarize some common characterization methods for the detection of oxygen vacancy, such as Raman, electron paramagnetic resonance (EPR), positron annihilation lifetime spectra (PALS), solid state nuclear magnetic resonance (ss-NMR), X-ray photoelectron spectroscopy (XPS), scanning tunneling microscope (STM), etc. The analysis of various characterization results is also illustrated by examples. On this basis, some opinions on the future development of oxygen vacancy characterization technology are proposed. It is hoped that it can provide support for the characterization and research of defects related to rare earth cerium-based catalytic materials.

Key words: oxygen vacancy, characterization techniques, catalyst, CeO₂, nanostructure, surface

中图分类号:

O 657

孙敬方, 葛成艳, 安冬琦, 仝庆, 高飞, 董林. 稀土铈基催化材料氧空位的表征方法综述[J]. 化工学报, 2020, 71(8): 3403-3415.

Jingfang SUN, Chengyan GE, Dongqi AN, Qing TONG, Fei GAO, Lin DONG. Review on characterization methods of oxygen vacancy in rare earth cerium-based catalysts[J]. CIESC Journal, 2020, 71(8): 3403-3415.

图/表 13

图1 离子掺杂后CeO2的晶体结构图

Fig.1 Crystal structure of doped ceria

表1 不同暴露晶面CeO2氧空位生成能[26]

Table 1 Oxygen vacancy formation energy of each surface of ceria[26]

Surface	M₁	ΔE_vac/eV	ΔQ_M1/e	ΔQ_M2/e	ΔQ_M3/e	ΔQ_M4/e	$Δ E v a c'$ /eV
(111)	Ce	+2.76	+0.32	+0.32	0.00	+0.06	+3.01
	Zr	+1.63	+0.02	+0.32	+0.28	+0.06	+2.02
	Pd	+0.71	+0.43	+0.05	+0.05	+0.03	+2.78
(110)	Ce	+2.10	+0.32	+0.32	-0.01	-0.01	+3.91
	Zr	+1.24	+0.08	+0.31	+0.26	+0.06	+4.78
	Pd	-0.09	+0.38	+0.06	+0.04	+0.03	+0.82
(100)	Ce	+2.26	+0.35	+0.37	+0.02	+0.01	—
	Zr	+1.84	+0.07	+0.30	+0.26	+0.03	—
	Pd	-0.05	+0.51	+0.08	+0.01	+0.02	—

表1 不同暴露晶面CeO2氧空位生成能[26]

Table 1 Oxygen vacancy formation energy of each surface of ceria[26]

Surface	M₁	ΔE_vac/eV	ΔQ_M1/e	ΔQ_M2/e	ΔQ_M3/e	ΔQ_M4/e	$Δ E v a c'$ /eV
(111)	Ce	+2.76	+0.32	+0.32	0.00	+0.06	+3.01
	Zr	+1.63	+0.02	+0.32	+0.28	+0.06	+2.02
	Pd	+0.71	+0.43	+0.05	+0.05	+0.03	+2.78
(110)	Ce	+2.10	+0.32	+0.32	-0.01	-0.01	+3.91
	Zr	+1.24	+0.08	+0.31	+0.26	+0.06	+4.78
	Pd	-0.09	+0.38	+0.06	+0.04	+0.03	+0.82
(100)	Ce	+2.26	+0.35	+0.37	+0.02	+0.01	—
	Zr	+1.84	+0.07	+0.30	+0.26	+0.03	—
	Pd	-0.05	+0.51	+0.08	+0.01	+0.02	—

图2 不同铈盐前体制备CeO2样品的拉曼结果[37]

Fig.2 Raman results of CeO2 prepared from different precursors[37]

图3 从紫外拉曼、可见拉曼及XRD表征中可以得到的样品信息[38]

Fig.3 Sample information obtained by UV Raman, visible Raman and XRD pattern[38]

图4 (a)不同温度还原后CeO2纳米棒在室温的O2吸附拉曼结果[39]; (b) CeO2纳米颗粒与H2O2反应拉曼结果[43]

Fig.4 (a) Raman spectra of O2 adsorption at room temperature on different temperature reduced ceria nanorodsm[39]; (b) Raman spectra of CeO2 nanoparticles during the reaction with H2O2[43]

表2 预先吸附O2后的样品在773 K下的EPR结果[46]

Table 2 Characteristic of the EPR signals obtained upon oxygen adsorption on the samples outgessed at 773 K[46]

Signal	EPR parameters	Proposed assignment
OC1 type	g_z = 2.031—2.030, g_x = 2.017, g_y = 2.011	Ce⁴⁺-O₂^- species formed on isolated vacancies of three-dimensional particles
OC1 type	g_‖= 2.034—2.032, g_⊥= 2.011—2.010
OC2	g_z = 2.042—2.039, g_x = 2.009—2.008	Ce⁴⁺-O₂^- species formed on isolated vacancies of three-dimensional particles
OC2	g_y = 2.010—2.009
OCZ	g_z = 2.026—2.025, g_x = 2.018—2.017	Ce⁴⁺-O₂^- species formed on two-dimensional ceria-type patches
OCZ	g_y = 2.011
OZ	g_z = 2.037, 2.032, g_y = 2.009	Zr⁴⁺-O₂^- species
OZ	g_x = 2.002	Zr⁴⁺-O₂^- species

图5 773 K下先抽真空再O2吸附后的样品在77 K下的EPR结果[47]

Fig.5 EPR spectra at 77 K following oxygen adsorption at room temperature on the sample out gassed at 773 K[47]

表3 不同样品的PALS峰拟合结果和Raman结果[52]

Table 3 Peak-fitting results of PALS spectra and Raman spectra of various samples[52]

Sample	τ₁/ps	τ₂/ps	τ₃/ps	I₁/%	I₂/%	I₃/%	I₂/I₁
c-CeO₂	187.0	350.2	1.50	35.99	63.16	0.85	1.75
1%-Ag/ c-CeO₂	203.3	366.1	2.10	42.82	56.48	0.70	1.32
3%-Ag/ c-CeO₂	198.9	360.7	1.74	40.6	58.5	0.9	1.44
r-CeO₂	262.0	397.0	1.90	31.2	67.9	0.9	2.18
1%-Ag/ r-CeO₂	230.2	384.7	1.71	21.72	77.06	1.22	3.55
3%-Ag/ r-CeO₂	250.2	409.3	2.36	41.5	57.5	1.0	1.39

图6 17O2富集后不同形貌CeO2的ss-NMR结果[57]

Fig.6 ss-NMR results of CeO2 with different morphologies after 17O2 enrichment[57]

图7 不同形貌CeO2的DNP增强ss-NMR结果[57]

Fig.7 DNP enhanced ss-NMR results of CeO2 with different morphologies[57]

图8 CeO2和CeO2/Co3O4的Ce 3d高分辨XPS结果(a)，CeO2和CeO2/Co3O4的O 1s(b)和 Co 2p (c) XPS结果，CeO2和CeO2/Co3O4的Co L-edge XANES结果(d) [63]

Fig.8 High-resolution Ce 3d XPS spectra of CeO2 and CeO2/Co3O4(a). High-resolution O 1s (b) and Co 2p (c) XPS spectra of CeO2 and CeO2/Co3O4. Co L-edge XANES of CeO2 and CeO2/Co3O4 (d) [63]

图9 CuO-CeO2催化剂的Ce 3d XPS结果[67]

Fig.9 Ce 3d XPS spectra of CuO-CeO2 catalysis[67]

图10 900℃加热1 min(a)和5 min(b)后的CeO2(111)面的STM结果以及对应出现的各种氧空位信息。由图(a)和图(b)中统计出来的表面线性氧空位团簇（LSVC）分布图(c)[71]

Fig.10 STM images of the CeO2(111) surface obtained after 1 min (a) and 5 min (b) of annealing at 900℃, with corresponding representations of the observed defects. (c) Histogram of the LSVC distribution as evaluated from (a) (solid circles) and (b) (open squares)[71]

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