ZnZrOx固溶体催化剂表面羟基在CO2加氢制甲醇中的作用

doi:10.1016/S1872-2067(22)64176-7

催化学报 ›› 2023, Vol. 45: 162-173.DOI: 10.1016/S1872-2067(22)64176-7

ZnZrO_x固溶体催化剂表面羟基在CO₂加氢制甲醇中的作用

沙峰^a^,^b, 唐珊^a^,^c, 汤驰洲^a^,^c, 冯振东^a^,^c, 王集杰^a^,^*(), 李灿^a^,^c^,^*()

^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南开大学材料科学与工程学院, 国家新材料研究院, 天津300350
^c中国科学院大学, 北京100049

收稿日期:2022-07-25 接受日期:2022-09-17 出版日期:2023-02-18 发布日期:2023-01-10
通讯作者: 王集杰,李灿
基金资助:
中国科学院战略先导科技专项(XDA21090202);人工光合成基础科学中心(FReCAP);人工光合成基础科学中心(22088102);国家自然科学基金(22172160)

The role of surface hydroxyls on ZnZrO_x solid solution catalyst in CO₂ hydrogenation to methanol

Feng Sha^a^,^b, Shan Tang^a^,^c, Chizhou Tang^a^,^c, Zhendong Feng^a^,^c, Jijie Wang^a^,^*(), Can Li^a^,^c^,^*()

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, Liaoning, China
^bSchool of Materials Science and Engineering and National Institute for Advanced Materials, Nankai University, Tianjin, 300350, China
^cUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2022-07-25 Accepted:2022-09-17 Online:2023-02-18 Published:2023-01-10
Contact: Jijie Wang, Can Li
Supported by:
Transformational Technologies for Clean Energy and Demonstration(XDA21090202);Fundamental Research Center of Artificial Photosynthesis(FReCAP);Fundamental Research Center of Artificial Photosynthesis(22088102);National Natural Science Foundation of China(22172160)

摘要/Abstract

摘要：

CO₂大量排放导致的全球气候变化对人类社会的发展造成不利影响, 控制CO₂排放是摆在全人类面前的一项紧迫任务. 利用太阳能等可再生能源获得的绿氢将CO₂转化为以甲醇为代表的燃料和化学品, 即太阳燃料合成, 不仅能够实现CO₂的减排利用, 而且能够将可再生能源储存于液体燃料, 对缓解全球气候变化和能源危机具有重要的战略意义. CO₂加氢制甲醇是衔接当下化石能源时代和未来可再生能源时代的重要桥梁, 亦是实现碳达峰、碳中和目标切实可行的路径之一. 高效、稳定的CO₂加氢制甲醇催化剂是实现这条路径的关键因素. 在众多催化剂中, 以ZnZrO_x为代表的固溶体催化剂因具有高甲醇选择性、良好热稳定性、可抗硫中毒特性而备受关注. 因此, 设计和开发更高效的ZnZrO_x固溶体催化剂对于CO₂加氢制甲醇规模化应用尤为重要.
本文分别利用蒸氨法和共沉淀法制得了相同组成的ZnZrO_x固溶体催化剂, 并用于催化CO₂加氢制甲醇. 结果表明, 蒸氨法制得的ZnZrO_x-RA催化剂比共沉淀法制得的ZnZrO_x-CP催化剂在低温下对甲醇合成更高效, 且ZnZrO_x-RA催化剂在连续运行100 h后没有表现出失活迹象. 动力学分析结果表明, ZnZrO_x-RA催化剂具有更低的甲醇合成表观活化能和更高的CO生成表观活化能, H₂和CO₂的反应级数分别接近一级和零级, 并且高H₂分压和低CO₂分压有利于甲醇合成. X射线粉末衍射、高分辨透射电子显微镜、紫外可见漫反射、X射线光电子能谱、傅里叶变换红外和CO程序升温脱附等表征结果表明, ZnZrO_x-RA和ZnZrO_x-CP催化剂均以固溶体形式存在, 但前者表面富含更多以Zn-OH形式存在的羟基. H₂和CO₂程序升温脱附以及氘气-氢气同位素交换结果表明, ZnZrO_x-RA催化剂上的H₂和CO₂吸附能力强于ZnZrO_x-CP催化剂, 且ZnZrO_x-RA催化剂具有更强的H₂解离活化能力. 原位红外实验表明, ZnZrO_x-RA催化剂上CO₂经HCOO*和H₃CO*中间体加氢生成甲醇, 且ZnZrO_x-RA催化剂上的HCOO*和H₃CO*物种浓度显著高于ZnZrO_x-CP催化剂. ZnZrO_x-RA催化剂中的Zn-OH不仅能促进H₂和CO₂的吸附与活化, 而且能促进HCOO*物种生成以及稳定所生成的HCOO*物种, 从而促进CO₂高选择性地加氢制甲醇. 综上, 本文为合理设计CO₂加氢制甲醇催化剂提供了新思路.

关键词: 表面羟基, ZnZrO_x固溶体, 二氧化碳加氢, 甲醇合成, 制备方法

Abstract:

ZnZrO_x solid solution catalyst is an excellent catalyst in methanol synthesis from CO₂ hydrogenation. It is still highly aspiration to make any further improvement in catalytic performance. In this work, ZnZrO_x solid solution catalyst is prepared with different methods, resulting in different surface property. The ZnZrO_x solid solution catalyst prepared by reflux ammonia (ZnZrO_x-RA) exhibits higher methanol selectivity of 95.2% and CO₂ conversion of 3.3% than that of the catalyst obtained via co-precipitation (ZnZrO_x-CP) at 280 °C, 5 MPa. Subsequent kinetics analysis shows that ZnZrO_x-RA, in comparison to ZnZrO_x-CP, shows a decreased activation energy for methanol synthesis, an increased reaction order in H₂, and a similar reaction order in CO₂. Structural characterizations indicate that these two catalysts are in solid solution state, while ZnZrO_x-RA possesses more Zn-OH species on the surface. The surface Zn-OH species enhance the activation and adsorption of CO₂ and H₂, and improve the generation and stability of HCOO* species, which promote CO₂ hydrogenation to methanol.

Key words: Surface hydroxyl, ZnZrOx solid solution, CO2 hydrogenation, Methanol synthesis, Preparation method

沙峰, 唐珊, 汤驰洲, 冯振东, 王集杰, 李灿. ZnZrO_x固溶体催化剂表面羟基在CO₂加氢制甲醇中的作用[J]. 催化学报, 2023, 45: 162-173.

Feng Sha, Shan Tang, Chizhou Tang, Zhendong Feng, Jijie Wang, Can Li. The role of surface hydroxyls on ZnZrO_x solid solution catalyst in CO₂ hydrogenation to methanol[J]. Chinese Journal of Catalysis, 2023, 45: 162-173.

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图/表 9

Fig. 1. CO2 conversion and methanol selectivity (a), and methanol STY (b) over different catalysts. (c) Stability test of ZnZrOx-RA at 320 °C. Reaction conditions: 280-340 °C, 5 MPa, H2/CO2 = 3:1, and 24000 mL·gcat-1·h-1.

Fig. 2. CO2 conversion (a), methanol selectivity (b), and methanol STY (c) as a function of the molar ratio of H2/CO2 in the feed gas over ZnZrOx-RA catalyst. Reaction conditions: 260-340 °C, 5 MPa, and 24000 mL·gcat-1·h-1.

Fig. 3. CO2 conversion (a), methanol selectivity (b), and methanol STY (c) as a function of space velocity over ZnZrOx-RA catalyst. Reaction conditions: 290 °C, 5 MPa, H2/CO2=6:1, and 24000 mL·gcat-1·h-1.

Fig. 4. Arrhenius plot for CO2 hydrogenation to methanol (a) and the RWGS reaction (b), and dependence of methanol formation rate on H2 partial pressure (c) and CO2 partial pressure (d) over ZnZrOx-RA and ZnZrOx-CP catalysts.

Fig. 5. XRD patterns of ZnZrOx-RA and ZnZrOx-CP catalysts.

Fig. 6. HRTEM and EDX element mapping of ZnZrOx-RA (a-c) and ZnZrOx-CP (d-f) catalysts.

Fig. 7. UV-vis (a), XPS of Zn 2p (b), FT-IR spectra (c), and CO-TPD profiles (d) for ZnZrOx-RA and ZnZrOx-CP catalysts.

Fig. 8. H2-TPR (a), H2-D2 exchange (b), H2-TPD (c), and CO2-TPD (d) profiles for ZnZrOx-RA and ZnZrOx-CP catalysts.

Fig. 9. In situ DRIFT spectra of ZnZrOx-RA and ZnZrOx-CP in the range of 3200-2700 cm-1 under different atmosphere H2 + CO2 (a), H2 (b), and 1 MPa H2 (c), and variation of IR peak intensities of HCOO* (d), CH3O* (e), and dynamic change of the HCOO*/CH3O ratio (f) over ZnZrOx-RA and ZnZrOx-CP catalysts.

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ZnZrO_x固溶体催化剂表面羟基在CO₂加氢制甲醇中的作用

The role of surface hydroxyls on ZnZrO_x solid solution catalyst in CO₂ hydrogenation to methanol

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