负载型Cu/Al2O3和Cu/ZnO催化剂上CO2加氢的原位FTIR及准原位XPS/HS-LEIS研究

doi:10.1016/S1872-2067(20)63672-5

催化学报 ›› 2021, Vol. 42 ›› Issue (3): 367-375.DOI: 10.1016/S1872-2067(20)63672-5

• 论文 • 下一篇

负载型Cu/Al₂O₃和Cu/ZnO催化剂上CO₂加氢的原位FTIR及准原位XPS/HS-LEIS研究

胡俊, 李洋洋, 郑燕萍, 陈明树^*(), 万惠霖

厦门大学化学化工学院,固体表面物理化学国家重点实验室,醇醚酯化工清洁生产国家工程实验室,福建厦门361005

收稿日期:2020-05-23 接受日期:2020-06-28 出版日期:2021-03-18 发布日期:2021-01-23
通讯作者: 陈明树
基金资助:
国家自然科学基金(21872110);国家自然科学基金(91545204);国家自然科学基金(21573180)

In situ FTIR and ex situ XPS/HS-LEIS study of supported Cu/Al₂O₃ and Cu/ZnO catalysts for CO₂ hydrogenation

Jun Hu, Yangyang Li, Yanping Zhen, Mingshu Chen^*(), Huilin Wan

State Key Laboratory of Physical Chemistry of Solid Surfaces,National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters,Department of Chemistry,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,Fujian,China

Received:2020-05-23 Accepted:2020-06-28 Online:2021-03-18 Published:2021-01-23
Contact: Mingshu Chen
About author:^*Tel/Fax:+86‐592‐2183723;E‐mail:chenms@xmu.edu.cn
Supported by:
National Natural Science Foundation of China(21872110);National Natural Science Foundation of China(91545204);National Natural Science Foundation of China(21573180)

摘要/Abstract

摘要：

铜基催化剂是工业合成甲醇中常用的催化剂,其主要包含Cu,ZnO,Al₂O₃三种组分,研究各组分在催化合成甲醇过程中的本质作用及其相互间的协同作用不仅是一个催化基础科学问题,同时对于设计和合成新型高性能的铜基催化剂也有重要指导作用. 以往的研究主要针对Cu和ZnO二元组分,关于Al₂O₃的作用很少有报道,主要观点认为Al₂O₃起结构助剂的作用. 在Cu/Al₂O₃/ZnO(0001)-Zn模型催化体系的研究中,我们发现Al₂O₃具有稳定Cu⁺的能力. 为了更接近于实际催化体系,并进一步探索铜基催化剂中载体Al₂O₃及ZnO的作用,我们制备了负载型的5 wt% Cu/Al₂O₃及5 wt% Cu/ZnO催化剂,并通过原位傅里叶变换红外光谱(in situ FTIR)、准原位X射线光电子能谱(ex situ XPS)及高灵敏度低能离子散射谱(HS-LEIS),着重考察H₂还原及CO₂加氢过程中表面吸附物种的转变及催化剂表面结构变化,更深一步理解Cu,ZnO,Al₂O₃三组分在催化CO₂加氢过程中所起的作用及相互间的协同作用. 通过XRD,BET和TEM表征,发现采用浸渍负载法制备的、经过焙烧后的5 wt% Cu/Al₂O₃及5 wt% Cu/ZnO催化剂的结构和形貌有明显差别,Al₂O₃载体具有较大的比表面积,CuO在其表面分散性较好,而ZnO的比表面积很小、CuO颗粒也相对较大. Ex situ XPS及HS-LEIS显示,经过H₂还原后,Cu在Al₂O₃表面的颗粒粒径略有增大,表面仍有较大比例的Cu⁺物种. 以CO为探针分子的FTIR光谱也表明,H₂还原后5 wt% Cu/Al₂O₃存在一定量的Cu⁺,而5 wt% Cu/ZnO催化剂还原后形成Cu纳米粒子表面被ZnO_x包覆,ex situ XPS及HS-LEIS的深度剖析也证实了上述结果. CO₂加氢过程中,5 wt% Cu/Al₂O₃表面能够形成大量碳酸氢盐及碳酸盐物种并在升温过程中逐渐转变为甲酸盐,表面仍有一定量的Cu⁺; 5 wt% Cu/ZnO表面形成的碳酸盐及碳酸氢盐物种含量相对较少,但Cu-ZnO_x的协同作用形成活化H₂的高活性表面,在室温下就可以生成甲酸盐物种,在随后的升温过程中甲酸盐逐渐转变为甲氧基. 通过对比负载型Cu/Al₂O₃及Cu/ZnO催化剂的研究,得以更加深入地理解铜基催化剂中载体在CO₂加氢制甲醇过程中所起的作用: Al₂O₃能较好分散Cu,且能够稳定Cu⁺; 相对于ZnO,Al₂O₃具有较强的吸附CO₂能力,能够在表面形成大量的碳酸氢盐物种及碳酸氢盐物种,与表面Cu作用在升温过程中能够生成大量的甲酸盐物种;对于5 wt% Cu/ZnO在H₂还原和CO₂加氢过程中Cu表面被ZnO_x包覆,其高度缺陷的表面结构能在室温下解离H₂.这些结果表明,实际CuZnAlO催化剂上CO₂加氢制备甲醇的活性位点可能包含Cu⁺,Cu⁰及相邻的具有高度缺陷结构的ZnO_x包覆层.

关键词: 铜基催化剂, 原位FTIR, 准原位XPS/HS-LEIS, CO₂加氢, ZnO_x覆盖层

Abstract:

Cu-based catalysts are commonly used in industry for methanol synthesis. In this study,supported catalysts of 5 wt% Cu/Al2O3 and 5 wt% Cu/ZnO were prepared,and their surface characteristics during H2 reduction and CO2 hydrogenation were investigated using in situ Fourier transform infrared spectroscopy (FTIR),ex situ X-ray photoelectron spectroscopy,and high sensitivity low energy ion scattering spectroscopy. During the H2 reduction and CO2 hydrogenation processes,it was found that Al2O3 can stabilize Cu+. In situ FTIR spectra indicated that the 5 wt% Cu/Al2O3 can adsorb large amounts of bicarbonate and carbonate species,which then convert into formate during CO2 hydrogenation. For the 5 wt% Cu/ZnO,it was found that Cu nanoparticles were gradually covered by a highly defective ZnOx overlayer during H2 reduction,which can effectively dissociate H2. During CO2 hydrogenation,the adsorbed bicarbonate or carbonate species can convert into formate and then into a methoxy species. Using these surface sensitive methods,a more in-depth understanding of the synergistic effect among the Cu,Al2O3,and ZnO components of Cu-based catalysts was achieved.

Key words: Cu-based catalyst, in situ FTIR, ex situ XPS/HS-LEIS, CO2 hydrogenation, ZnOx overlayer

胡俊, 李洋洋, 郑燕萍, 陈明树, 万惠霖. 负载型Cu/Al₂O₃和Cu/ZnO催化剂上CO₂加氢的原位FTIR及准原位XPS/HS-LEIS研究[J]. 催化学报, 2021, 42(3): 367-375.

Jun Hu, Yangyang Li, Yanping Zhen, Mingshu Chen, Huilin Wan. In situ FTIR and ex situ XPS/HS-LEIS study of supported Cu/Al₂O₃ and Cu/ZnO catalysts for CO₂ hydrogenation[J]. Chinese Journal of Catalysis, 2021, 42(3): 367-375.

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https://www.cjcatal.com/CN/Y2021/V42/I3/367

图/表 9

Fig. 1. Powder X-ray diffraction XRD patterns after calcination of Al2O3 and 5 wt% Cu/Al2O3 (a) and ZnO and 5 wt% Cu/ZnO (b). The rhombus marks represent the diffraction peaks of CuO.

Fig. 2. N2 adsorption-desorption isotherms and the corresponding pore size distribution curves (inset) for Al2O3,5 wt% Cu/Al2O3,ZnO,and 5 wt% Cu/ZnO.

Fig. 3. CO adsorption bands of (a) the 5 wt% Cu/Al2O3 and (b) the 5 wt% Cu/ZnO after different treatments ([O],[V],and [H] are representative of the O2 oxidization,evacuation,and H2 reduction processes,respectively; PO2 = 100 Torr and PH2 = 100 Torr).

Fig. 4. XPS spectra of Cu 2p (a),Cu L3M4.5M4.5 (b); (c) XPS intensity ratio of Cu0,Cu+,and Cu2+ after the O2 oxidization and H2 reduction processes ([O] and [H] are representative of O2 oxidization and H2 reduction processes,respectively; PO2 = 1 atm and PH2 = 1 atm).

Fig. 5. XPS spectra of Cu 2p (a) and Cu L3M4.5M4.5 (b) after O2 oxidization and H2 reduction processes ([O] and [H] are representative of O2 oxidization and H2 reduction processes,respectively; PO2 = 1 atm and PH2 = 1 atm).

Fig. 6. In situ FTIR spectra of the 5 wt% Cu/Al2O3 (a,b) and the 5 wt%Cu/ZnO (c,d) during CO2 hydrogenation reactions (PCO2 = 33 Torr and PH2 = 100 Torr) at different temperatures after pre‐reduction by H2 at 523 K (PH2 = 100 Torr).

Table 1 IR band assignments for the adsorption species on Al2O3,ZnO,and Cu.

Adsorbed species	Band (cm^-1)	Assignment	Ref.
Bicarbonate on Al₂O₃	1658 1424-1439 1227	ν_as(OCO) ν_s(OCO) δ(OH)	[51-53]
Monodentate carbonate on Al₂O₃	1480 1390 1077	ν_as(OCO) ν_s(OCO) ν(CO)	[54,55]
Polydentate carbonate on Al₂O₃	1525 1330	ν_as(OCO) ν_s(OCO)	[56]
Bidentate formate on Al₂O₃	1592 1377 1393 2769 2904 2999	ν_as(OCO) ν_s(OCO) δ(C-H) δ(C-H) + ν_s(OCO) ν(C-H) δ(C-H) + ν_as(OCO)	[51,57,58]
Bicarbonate on ZnO	1634 1418 1225	ν_as(OCO) ν_s(OCO) δ(OH)	[59,60]
Bidentate carbonate on ZnO	1606 1343	ν_as(OCO) ν_s(OCO)	[56,59]
Polydentate carbonate on ZnO	1513 1326	ν_as(OCO) ν_s(OCO)	[56,61]
Uncoordinated carbonate on ZnO	1445	ν_as(OCO)	[62]
Bidentate formate on ZnO	1576 1382 1365 2876 2970	ν_as(OCO) δ(C-H) ν_s(OCO) ν(C-H) δ(C-H)+ ν_as(OCO)	[61-63]
Methoxy on ZnO	2930 2815 1050	ν_as(CH₃) ν_s(CH₃) ν(C-O)	[31,62,63]
Bidentate formate on Cu	1636 1328 1354 2745 2855 2929	ν_as(OCO) ν_s(OCO) δ(C-H) δ(C-H) + ν_s(OCO) ν(C-H) δ(C-H)+ ν_as(OCO)	[51,63]

Fig. 7. XPS spectra of Cu 2p (a),Cu L3M4.5M4.5 (b); (c) the XPS intensity ratios of Cu0,Cu+,Cu2+; (d) the corresponding HS-LEIS spectra; (e) the top surface content of Cu after H2 pre-reduction and CO2 hydrogenation reactions for the 5 wt% Cu/Al2O3 (PH2 = 1 atm during 523 K H2 pre-reduction,PCO2 = 0.33 atm,and PH2 = 0.67 atm during CO2 hydrogenation reactions).

Fig. 8. In situ FTIR spectra of the 5 wt% Cu/ZnO-Al2O3 (Zn/Al molar ratio of 3) during CO2 hydrogenation reactions (PCO2 = 33 Torr and PH2 = 100 Torr) after pre-reduction by 100 Torr H2 at 523 K.

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负载型Cu/Al₂O₃和Cu/ZnO催化剂上CO₂加氢的原位FTIR及准原位XPS/HS-LEIS研究

In situ FTIR and ex situ XPS/HS-LEIS study of supported Cu/Al₂O₃ and Cu/ZnO catalysts for CO₂ hydrogenation

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