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Study on synthesis of ZnO/ZrO2 catalyst and its application in CO2 hydrogenation to methanol
Received date: 2024-10-16
Online published: 2024-11-25
Direct hydrogenation of CO2 to methanol provides a viable method for the fixation of CO2，and also offers a strategy for storing hydrogen.In this study，a series of ZnO/MO x （M=Zr，Ti） catalysts for CO2 hydrogenation to methanol were synthesized by hydrothermal and co⁃precipitation methods，respectively.The activity evaluation indicated that 20%ZnO/ZrO2-C catalyst prepared by co⁃precipitation method exhibited the most excellent activation with a CO2 conversion of 9.0%，a methanol selectivity of 58.3%，while the methanol space time yield up to 0.321 g/（g·h） under the condition of 350 ℃，3.0 MPa and 24 000 mL/（g·h）.A series of structural characterizations were conducted，including X-ray powder diffraction，scanning electron microscopy，transmission electron microscopy，H2 temperature⁃programmed reduction，N2 adsorption⁃desorption，X-ray photoelectron spectroscopy and CO2 temperature⁃programmed desorption.It was demonstrated that 20%ZnO/ZrO2-C existed in the form of a solid solution state，which possessed relatively more uniform mesoporous structure，larger specific surface area，lower reduction temperature and high CO2 activation capability.It indicated that the ZnO-ZrO2 interface could be beneficial for methanol synthesis.The appropriate amount of ZnO was conducive to generating more ZnO-ZrO2 interface，thereby enhancing catalytic performance.
Key words： methanol synthesis; ZnO/ZrO2 solid solution; catalysts; CO2 hydrogenation
ZHANG Peipei , WANG Wenbo , MI Xiaotong , XIN Jing , LI Yongheng , LI Sixuan , XIA Lin . Study on synthesis of ZnO/ZrO2 catalyst and its application in CO2 hydrogenation to methanol[J]. Inorganic Chemicals Industry, 2025 , 57(5) : 125 -132 . DOI: 10.19964/j.issn.1006-4990.2024-0552
| 1 | KARL T R， TRENBERTH K E.Modern global climate change［J］.Science，2003，302（5651）：1719-1723. |
| 2 | SONG Chunshan.Global challenges and strategies for control，conversion and utilization of CO2 for sustainable development involving energy，catalysis，adsorption and chemical processing［J］.Catalysis Today，2006，115（1/2/3/4）：2-32. |
| 3 | ZHAO Huibo， LIU Xiaochen， ZENG Chunyang，et al.Thermochemical CO2 reduction to methanol over metal?based single?atom catalysts（SACs）：Outlook and challenges for developments［J］.Journal of the American Chemical Society，2024，146（34）：23649-23662. |
| 4 | WEI Jian， GE Qingjie， YAO Ruwei，et al.Directly converting CO2 into a gasoline fuel［J］.Nature Communications，2017，8：15174. |
| 5 | STUDT F， SHARAFUTDINOV I， ABILD-PEDERSEN F，et al.Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol［J］.Nature Chemistry，2014，6（4）：320-324. |
| 6 | CHEN Fei， ZHANG Peipei， ZENG Yan，et al.Vapor?phase low?temperature methanol synthesis from CO2-containing syngas via self?catalysis of methanol and Cu/ZnO catalysts prepared by solid?state method［J］.Applied Catalysis B：Environmental，2020，279：119382. |
| 7 | LI Hangjie， FANG Wei， WANG Lingxiang，et al.Physical regulation of copper catalyst with a hydrophobic promoter for enhancing CO2 hydrogenation to methanol［J］.Innovation，2023，4（4）：100445. |
| 8 | LI Hangjie， XIAO Yuehua， XIAO Jiale，et al.Selective hydrogenation of CO2 into dimethyl ether over hydrophobic and gallium?modified copper catalysts［J］.Chinese Journal of Catalysis，2023，54：178-187. |
| 9 | ZHANG Peipei， ARAKI Y， FENG Xiaobo，et al.Urea?derived Cu/ZnO catalyst being dried by supercritical CO2 for low?temperature methanol synthesis［J］.Fuel，2020，268：117213. |
| 10 | ZHAO Huibo， YU Ruofan， MA Sicong，et al.The role of Cu1-O3 species in single?atom Cu/ZrO2 catalyst for CO2 hydrogenation［J］.Nature Catalysis，2022，5（9）：818-831. |
| 11 | RUNGTAWEEVORANIT B， BAEK J， ARAUJO J R，et al.Copper nanocrystals encapsulated in Zr-based metal?organic frameworks for highly selective CO2 hydrogenation to methanol［J］.Nano Letters，2016，16（12）：7645-7649. |
| 12 | GAO Peng， LI Feng， ZHAN Haijuan，et al.Influence of Zr on the performance of Cu/Zn/Al/Zr catalysts via hydrotalcite?like precursors for CO2 hydrogenation to methanol［J］.Journal of Catalysis，2013，298：51-60. |
| 13 | LI Hangjie， WANG Liang， XIAO Fengshou.Importance of zeolite in multifunctional catalysts for syngas conversion［J］.Carbon Future，2024，1（1）：9200003. |
| 14 | YANG Meng， YU Jiafeng， ZIMINA A，et al.Unlocking a dual?channel pathway in CO2 hydrogenation to methanol over single?site zirconium on amorphous silica［J］.Angewandte Chemie International Edition，2024，63（4）：e202312292. |
| 15 | WANG Xiaoyu， YAO Zhengyang， GUO Xiaohong，et al.Modulating electronic interaction over Zr-ZnO catalysts to enhance CO2 hydrogenation to methanol［J］.ACS Catalysis，2024，14（1）：508-521. |
| 16 | REDEKOP E A， CORDERO-LANZAC T， SALUSSO D，et al.Zn redistribution and volatility in ZnZrO x catalysts for CO2 hydrogenation［J］.Chemistry of Materials，2023，35（24）：10434-10445. |
| 17 | ZHANG Fanxing， LI Boyang， QUAN Xu，et al.Revealing the dynamics of oxygen vacancy in ZnO1- x /Cu during robust methanol synthesis from CO2 ［J］.ACS Catalysis，2024，14（9）：7136-7148. |
| 18 | WANG Jijie， LI Guanna， LI Zelong，et al.A highly selective and stable ZnO-ZrO2 solid solution catalyst for CO2 hydrogenation to methanol［J］.Science Advances，2017，3（10）：e1701290. |
| 19 | WANG Jijie， TANG Chizhou， LI Guanna，et al.High?performance MaZrO x （Ma=Cd，Ga） solid?solution catalysts for CO2 hydrogenation to methanol［J］.ACS Catalysis，2019，9（11）：10253-10259. |
| 20 | XU Di， HONG Xinlin， LIU Guoliang.Highly dispersed metal doping to ZnZr oxide catalyst for CO2 hydrogenation to methanol：Insight into hydrogen spillover［J］.Journal of Catalysis，2021，393：207-214. |
| 21 | FENG Wenhua， YU Mingming， WANG Lijun，et al.Insights into bimetallic oxide synergy during carbon dioxide hydrogenation to methanol and dimethyl ether over GaZrO x oxide catalysts［J］.ACS Catalysis，2021，11（8）：4704-4711. |
| 22 | 任启霞，杨坤，刘飞，等.新助剂对ZnO/ZrO2物化性质及催化性能的影响［J］.无机盐工业，2024，56（3）：144-154. |
| REN Qixia， YANG Kun， LIU Fei，et al.Effect of promoter on physicochemical properties and catalytic performance of ZnO/ZrO2 ［J］.Inrganic Chemicals Industry，2024，56（3）：144-154. | |
| 23 | LEE K， DICKIESON M P， JUNG M，et al.Structure sensitivity of ZnZrO x catalysts in CO2 hydrogenation to methanol：Significance of surface oxygen content and synthesis strategy［J］.ACS Catalysis，2024，14（5）：3074-3089. |
| 24 | FENG Zhendong， TANG Chizhou， ZHANG Pengfei，et al.Asymmetric sites on the ZnZrO x catalyst for promoting formate formation and transformation in CO2 hydrogenation［J］.Journal of the American Chemical Society，2023，145（23）：12663-12672. |
| 25 | TING K W， TOYAO T， SIDDIKI S M A H，et al.Low?temperature hydrogenation of CO2 to methanol over heterogeneous TiO2-supported Re catalysts［J］.ACS Catalysis，2019，9（4）：3685-3693. |
| 26 | KATTEL S， YAN Binhang， YANG Yixiong，et al.Optimizing binding energies of key intermediates for CO2 hydrogenation to methanol over oxide?supported copper［J］.Journal of the American Chemical Society，2016，138（38）：12440-12450. |
| 27 | BANDO K K， SAYAMA K， KUSAMA H，et al. In?situ FT-IR study on CO2 hydrogenation over Cu catalysts supported on SiO2，Al2O3，and TiO2 ［J］.Applied Catalysis A：General，1997，165（1/2）：391-409. |
| 28 | WANG Jijie， MEEPRASERT J， HAN Zhe，et al.Highly dispersed Cd cluster supported on TiO2 as an efficient catalyst for CO2 hydrogenation to methanol［J］.Chinese Journal of Catalysis，2022，43（3）：761-770. |
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