ZnO/ZrO2催化剂的合成及其在CO2加氢制甲醇中的应用研究

doi:10.19964/j.issn.1006-4990.2024-0552

Abstract

Abstract:

Direct hydrogenation of CO₂ to methanol provides a viable method for the fixation of CO_2，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

CLC Number:

O643.36

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.

Figures/Tables 10

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References 28

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 ZnO_1- _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 M_aZrO _x （M_a=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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Study on synthesis of ZnO/ZrO₂ catalyst and its application in CO₂ hydrogenation to methanol

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Study on synthesis of ZnO/ZrO2 catalyst and its application in CO2 hydrogenation to methanol