CO2加氢制甲醇Cu/ZnO/Y2O3催化剂中Y2O3的作用

doi:10.1016/S1872-2067(24)60220-2

催化学报 ›› 2025, Vol. 70: 410-419.DOI: 10.1016/S1872-2067(24)60220-2

CO₂加氢制甲醇Cu/ZnO/Y₂O₃催化剂中Y₂O₃的作用

蔡子国^a, 于学峰^a, 王鹏龙^b, 吴慧芳^c, 种瑞峰^b, 任利敏^c, 胡涛^c, 王翔^a^,^*()

^a大连理工大学化工学院, 精细化工国家重点实验室, 辽宁大连 116024
^b河南大学化学与分子科学学院, 河南开封 475004
^c大连理工大学化学学院, 辽宁大连 116024

收稿日期:2024-11-12 接受日期:2024-12-24 出版日期:2025-03-18 发布日期:2025-03-20
通讯作者: * 电子信箱: xiangwang@dlut.edu.cn (王翔).
基金资助:
国家自然科学基金(22272016);国家自然科学基金(DUT21RC(3)113)

Role of Y₂O₃ in Cu/ZnO/Y₂O₃ catalysts for CO₂ hydrogenation to methanol

Ziguo Cai^a, Xuefeng Yu^a, Penglong Wang^b, Huifang Wu^c, Ruifeng Chong^b, Limin Ren^c, Tao Hu^c, Xiang Wang^a^,^*()

^aState Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
^bCollege of Chemistry and Molecular Sciences, Henan University, Kaifeng 475004, Henan, China
^cSchool of Chemistry, Dalian University of Technology, Dalian 116024, Liaoning, China

Received:2024-11-12 Accepted:2024-12-24 Online:2025-03-18 Published:2025-03-20
Contact: * E-mail: xiangwang@dlut.edu.cn (X. Wang).
Supported by:
National Natural Science Foundation of China(22272016);Fundamental Research Funds for the Central Universities(DUT21RC(3)113)

摘要/Abstract

摘要：

CO₂加氢制甲醇是碳的捕集、利用和封存中最具吸引力的策略之一. 甲醇不仅可用作燃料, 而且还是生产其他高附价值化学品(包括低碳烯烃、汽油、芳烃等)的基本原料. CuZn基催化剂因其成本低、活性高而受到广泛关注. 然而, Cu和ZnO颗粒在副产物水的作用下会发生烧结团聚, 从而导致甲醇选择性降低. Y₂O₃的引入中可提高催化剂的甲醇产率, 但其作用机理仍不清楚.

本文通过一锅水热法制备了Cu/ZnO, Cu/ZnO/Y₂O₃和Cu/Y₂O₃催化剂, 旨在阐明Y₂O₃在Cu/ZnO/Y₂O₃催化剂中的作用. 催化剂性能评价结果表明, 相比于Cu/ZnO和Cu/Y₂O₃催化剂, Cu/ZnO/Y₂O₃催化剂表现出最高的甲醇产率, 这可能归因于ZnO和Y₂O₃载体之间的协同效应. 比表面积测试结果表明, 在Cu/ZnO中引入Y₂O₃后, 催化剂的比表面积随着Y₂O₃引入量的增加而逐渐增大. 然而, 甲醇产率呈现出先增加后减少的趋势. 其中, 甲醇产率最高的Cu/ZnO/Y₂O₃催化剂的比表面积在所有催化剂中处于中等水平, 这说明比表面积并不是导致催化剂活性增加的主要原因. X射线衍射和H₂-程序升温还原结果表明, Y₂O₃的引入可以提高催化剂表面Cu物种的分散度以及增强其与载体之间的相互作用. 拉曼光谱、X射线光电子能谱和CO₂程序升温脱附结果表明, Y₂O₃的引入使催化剂表面产生了更多的氧空位, 从而增加了对CO₂物种的吸附和活化. 动力学分析和原位漫反射红外光谱结果表明, HCOO*中间物种为产物CO和甲醇的共同中间物种, 两者存在竞争. 在Cu/ZnO/Y₂O₃催化剂中, Y₂O₃的引入可以增大生成CO的能垒, 同时减小生成甲醇的能垒, 从而提高了催化剂上的甲醇产率.

综上所述, 本文发现Y₂O₃与ZnO之间的协同效应提高了甲醇的产率, 并阐明了Y₂O₃在催化剂中的作用及反应机理, 为高效催化剂的设计和对助剂的理解提供了一种新思路.

关键词: 甲醇产率, 氧空位, 动力学, 原位红外, 中间体

Abstract:

CuZn-based catalyst is an attractive catalyst for methanol synthesis from CO₂ hydrogenation, but it early deactivates and its methanol yield still needs to improve. In this study, Y₂O₃ was introduced to Cu/ZnO using a one-pot hydrothermal method, and exhibits a synergistic effect of ZnO and Y₂O₃ on enhancing methanol yield and the stability. We found that the interaction between Y₂O₃ and ZnO results in abundant oxygen vacancies formation, thereby enhancing CO₂ adsorption and activation. Kinetic analysis and in situ DRIFTS suggest that RWGS forming CO and methanol formation compete for a mutual intermediate HCOO^*, and the introduction of Y₂O₃ to Cu/ZnO raises the energy barrier for the CO formation but lowers that for methanol formation, thus enhancing the methanol yield on Cu/ZnO/Y₂O₃.

Key words: Methanol yield, Oxygen vacancies, Kinetics, Fourier transformed infrared, Intermediate

蔡子国, 于学峰, 王鹏龙, 吴慧芳, 种瑞峰, 任利敏, 胡涛, 王翔. CO₂加氢制甲醇Cu/ZnO/Y₂O₃催化剂中Y₂O₃的作用[J]. 催化学报, 2025, 70: 410-419.

Ziguo Cai, Xuefeng Yu, Penglong Wang, Huifang Wu, Ruifeng Chong, Limin Ren, Tao Hu, Xiang Wang. Role of Y₂O₃ in Cu/ZnO/Y₂O₃ catalysts for CO₂ hydrogenation to methanol[J]. Chinese Journal of Catalysis, 2025, 70: 410-419.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60220-2

https://www.cjcatal.com/CN/Y2025/V70/I3/410

图/表 9

Fig. 1. Performance of CuZnY-2 catalyst at 200-260 °C (a,b) and Cu/ZnO/Y2O3 catalysts with different ratios of ZnO to Y2O (c,d)3 at 240 °C in a mixture flow of H2/CO2/Ar = 3:1:1 under a pressure of 3 MPa with a GHSV of 9000 mL gcat.-1 h-1.

Fig. 2. SEM images of CuZn (a), CuY (b) and CuZnY-2 (c,d) catalysts. SEM-EDS elemental mapping images of (e-h) CuZnY-2 catalyst shown in (d).

Fig. 3. (a) XRD patterns of catalysts. (b) Raman spectra of calcined oxides and reduced catalysts. (c) Raman spectra of calcined, reduced, re-oxidation and re-reduction CuZnY-2. (d) O 1s XPS spectra of catalysts.

Fig. 4. (a) H2-TPR of CuZn-ox, CuZnY-2-ox and CuY-ox. (b) Cu 2p XPS spectra of CuZn, CuZnY-2 and CuY catalysts.

Fig. 5. Arrhenius plots for CH3OH formation (a) and CO formation (b), and H2 (c) and CO2 (d) reaction orders for CH3OH formation rate over CuY, CuZn and CuZnY-2 catalysts.

Fig. 6. (a) CO2-TPD of catalysts. (b) Proportion of moderate basic sites.

Fig. 7. In situ DRIFTS spectra collected when the feed gas was switched from Ar to CO2 over CuZnY-2 (Cu loading is 5%) catalyst at 240 °C and ambient pressure.

Fig. 8. In situ DRIFTS spectra collected at 240 °C and 1 bar when the feed gas was switched from H2 to CO2 (a), and then to H2 (c) over CuZnY-2 (Cu loading is 5%) catalyst. (b,d) Evolution of HCOO* species (2883 cm-1) and CH3O* species (2828 cm-1) with reaction time. (e) Scheme of reaction pathway for CO2 hydrogenation to methanol over Cu/ZnO/Y2O3.

Fig. 9. A 100-h test of CuZn and CuZnY-2 in CO2 hydrogenation at 240 °C in a mixture flow of H2/CO2/Ar = 3:1:1 under a pressure of 3 MPa with a GHSV of 9000 mL gcat-1 h-1.

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CO₂加氢制甲醇Cu/ZnO/Y₂O₃催化剂中Y₂O₃的作用

Role of Y₂O₃ in Cu/ZnO/Y₂O₃ catalysts for CO₂ hydrogenation to methanol

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