ZnO-CeO2制备及催化性能研究

doi:10.19964/j.issn.1006-4990.2023-0251

Abstract

Abstract:

The catalytic conversion of CO₂ to methanol using green hydrogen generated from renewable energy sources is a promising path toward carbon neutrality.The catalyst employed in the CO₂ hydrogenation to methanol technology is a ZnO-CeO₂ bimetallic oxide.Various preparation methods such as impregnation，co-precipitation，precipitation coating，and physical mixing were investigated.Characterization techniques including X-ray diffraction（XRD），N₂ adsorption-desorption，carbon dioxide temperature-programmed desorption（CO₂-TPD），hydrogen temperature-programmed desorption（H₂-TPD），scanning electron microscopy（SEM），and X-ray photoelectron spectroscopy（XPS） were utilized to analyze the physicochemical properties of the ZnO-CeO₂ bimetallic oxide catalyst and its impact on the catalytic performance in CO₂ hydrogenation to methanol.The results indicated that the preparation method significantly influenced the physicochemical properties and catalytic performance of the catalyst.The ZnO-CeO₂ catalyst prepared by co-precipitation exhibited excellent catalytic performance.Under reaction conditions of temperature of 300 ℃，pressure of 4 MPa，and weight hourly space velocity of 19 600 mL/（g·h），the CO₂ conversion rate reached 4.61%，methanol selectivity achieved 80.64%，and the methanol space-time yield reached 244.96 mg/（h·g）.It was observed that high concentration of oxygen vacancies，strong H₂ activation capability，large specific surface area，and pore volume were crucial for enhancing the catalytic performance of this catalyst.

Key words: CO₂ hydrogenation, methanol, bimetallic oxide, fixed bed, oxygen vacancy

CLC Number:

TQ132.41

ZHAN Sijin, LIU Shike, LIU Fei, YAO Mengqin, CAO Jianxin. Study on preparation and catalytic performance of ZnO-CeO₂[J]. Inorganic Chemicals Industry, 2024, 56(3): 137-143.

Figures/Tables 8

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References 26

1	张文沛.氧化亚铜改性材料的制备及其光（电）催化还原CO₂的性能研究［D］.武汉：华中师范大学，2015.
	ZHANG Wenpei.Fabrication of modified cuprous oxide materials and the photoelectrocatalytic CO₂ conversion to solar fuels［D］.Wuhan：Central China Normal University，2015.
2	钟成林.二氧化碳加氢合成甲醇Cu/TiO₂催化剂的研究［D］.上海：上海应用技术学院，2015.
	ZHONG Chenglin.Study of Cu/TiO₂ catalysts for methanol synthesis from CO₂ hydrogenation［D］.Shanghai：Shanghai Institute of Technology，2015.
3	YANG Yisen， TAN Zhonghao， WANG Sha，et al.Cu/Cu₂O nanocrystals for electrocatalytic carbon dioxide reduction to multi-carbon products［J］.Chemical Communications，2023，59（17）：2445-2448.
4	LIU Feng， ZHANG Bo， FANG Zhi，et al.Jet-to-jet interactions in atmospheric-pressure plasma jet arrays for surface processing［J］.Plasma Processes and Polymers，2018，15（1）：1700114.
5	NGUYEN-PHU H， KIM T， KIM Y，et al.Role of phase in NiMgAl mixed oxide catalysts for CO₂ dry methane reforming（DRM）［J］.Catalysis Today，2023，411/412：113894.
6	SHARIFIANJAZI F， ESMAEILKHANIAN A， AHMADI E，et al.Methane reforming in microchannels：Application to the methanol synthesis［J］.Chemical Engineering and Processing-Process Intensification，2023，185：109316.
7	AKBAR DARABADI Z ALI， MORTAZA Y， HOSSEIN N，et al.Low-carbon hydrogen，power and heat production based on steam methane reforming and chemical looping combustion［J］.Energy Conversion and Management，2023，279：156-170.
8	VALLURI S， CLAREMBOUX V， KAWATRA S.Opportunities and challenges in CO₂ utilization［J］.Journal of Environmental Scien- ces，2022，113：322-344.
9	CHANG Kuan， ZHANG Haochen， CHENG M J，et al.Application of ceria in CO₂ conversion catalysis［J］.ACS Catalysis，2020，10（1）：613-631.
10	YUAN Jing， YANG Manping， HU Qiaoli，et al.Cu/TiO₂ nanoparticles modified nitrogen-doped graphene as a highly efficient catalyst for the selective electroreduction of CO₂ to different alcohols［J］.Journal of CO₂ Utilization，2018，24：334-340.
11	SZANIAWSKA E， BIENKOWSKI K， RUTKOWSKA I A，et al.Enhanced photoelectrochemical CO₂-reduction system based on mixed Cu₂O-nonstoichiometric TiO₂ photocathode［J］.Catalysis Today，2018，300：145-151.
12	BAO Yunfeng， HUANG Chunlei， CHEN Limin，et al.Highly efficient Cu/anatase TiO₂｛001｝-nanosheets catalysts for methanol synthesis from CO₂ ［J］.Journal of Energy Chemistry，2018，27（2）：381-388.
13	ENSAFI A A， ALINAJAFI H A， REZAEI B.Pt-modified nitrogen doped reduced graphene oxide：A powerful electrocatalyst for direct CO₂ reduction to methanol［J］.Journal of Electroanalytical Chemistry，2016，783：82-89.
14	谢易欣.含过渡金属（M=Pt，Au，Cu，Zn）/石墨烯复合催化剂的设计合成及其电（光）催化性能［D］.福州：福建师范大学，2019.
	XIE Yixin.Design，synthesis and electrical（photo）catalytic performance of transition metal-containing（M=Pt，Au，Cu，Zn）/graphene composite catalysts［D］.Fuzhou：Fujian Normal University，2019.
15	WANG Xilong， ALABSI M H， ZHENG Peng，et al.PdCu supported on dendritic mesoporous Ce _x Zr_1- _x O₂ as superior catalysts to boost CO₂ hydrogenation to methanol［J］.Journal of Colloid and Interface Science，2022，611：739-751.
16	NIU Juntian， LIU Haiyu， JIN Yan，et al.Comprehensive review of Cu-based CO₂ hydrogenation to CH₃OH：Insights from experimental work and theoretical analysis［J］.International Journal of Hydrogen Energy，2022，47（15）：9183-9200.
17	张平，陈浩，陈林，等.基于NiZn层状双金属氢氧化物制备高效电催化CO₂还原的原子分散Ni-N-C催化剂［J］.催化学报（英文），2023，44（2）：152-161.
	ZHANG Ping， CHEN Hao， CHEN Lin，et al.Atomically dispersed Ni-N-C catalyst derived from NiZn layered double hydroxides for efficient electrochemical CO₂ reduction［J］.Chinese Journal of Catalysis，2023，44（2）：152-161.
18	SU Haiyan， MA Xiufang， SUN Chenghua，et al.A synergetic effect between a single Cu site and S vacancy on an MoS₂ basal plane for methanol synthesis from syngas［J］.Catalysis Science & Technology，2021，11（9）：3261-3269.
19	PACHOLIK G， ENZLBERGER L， BENZER A，et al. in situ XPS studies of MoS₂-based CO₂ hydrogenation catalysts［J］.Journal of Physics D：Applied Physics，2021，54（32）：324002.
20	HU Jingting， YU Liang， DENG Jiao，et al.Sulfur vacancy-rich MoS₂ as a catalyst for the hydrogenation of CO₂ to methanol［J］.Nature Catalysis，2021，4（3）：242-250.
21	CUI Pingping， SUN Ruyu， XIAO Linfei，et al.Exploring the effects of the interaction of carbon and MoS₂ catalyst on CO₂ hydrogenation to methanol［J］.International Journal of Molecular Sciences，2022，23（9）：5220.
22	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.
23	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.
24	WANG Weiwei， QU Zhenping， SONG Lixin，et al.CO₂ hydrogenation to methanol over Cu/CeO₂ and Cu/ZrO₂ catalysts：Tuning methanol selectivity via metal-support interaction［J］.Journal of Energy Chemistry，2020，40：22-30.
25	ZHANG Wenyu， WANG Sen， GUO Shujia，et al.Effective conversion of CO₂ into light olefins along with generation of low amoun-ts of CO［J］.Journal of Catalysis，2022，413：923-933.
26	TADA S， OCHIAI N， KINOSHITA H，et al.Active sites on Zn _x Zr_1– _x O_2– _x solid solution catalysts for CO₂-to-methanol hydrogenation［J］.ACS Catalysis，2022，12（13）：7748-7759.

催化剂	比表面积/（m²·g^-1）			孔容/（cm³·g^-1）
催化剂	S_BET	S_mic	S_mes	V_t	V_mic	V_mes
ZnO-CeO₂-IM	48	—	48	0.42	—	0.42
ZnO-CeO₂-PM	43	—	43	0.49	—	0.49
ZnO-CeO₂-CP	64	—	64	0.51	—	0.51
ZnO-CeO₂-PC	55	14	41	0.42	0.10	0.32
CeO₂	87	—	87	0.23	—	0.23

[1]	REN Qixia, YANG Kun, LIU Fei, YAO Mengqin, CAO Jianxin. Effect of promoter on physicochemical properties and catalytic performance of ZnO/ZrO₂ [J]. Inorganic Chemicals Industry, 2024, 56(3): 144-154.
[2]	YANG Kun, REN Qixia, DONG Yonggang, LIU Fei, YAO Mengqin, CAO Jianxin. Effect of calcination temperature on catalytic performance of ZnGaZrO _x /SAPO-34 [J]. Inorganic Chemicals Industry, 2024, 56(2): 136-145.
[3]	LI He, ZHANG Lijie, ZHANG Kai, SU Jin, YAO Zhaoyang, ZENG Xianjun, GUO Chunlei, SUN Yanmin. Advances in technology and catalyst for methanol oxidized to formaldehyde [J]. Inorganic Chemicals Industry, 2023, 55(11): 12-18.
[4]	YANG Tinglong,WANG Fuzhong,LIU Fei. Study on sulfur poisoning of zirconium-based bimetallic oxides catalyst [J]. Inorganic Chemicals Industry, 2023, 55(1): 151-158.
[5]	CHEN Jun,ZHONG Jing,LIN Sen,YU Jianguo. Study on lithium separation from brine by aluminum-based adsorbent in fixed bed [J]. Inorganic Chemicals Industry, 2023, 55(1): 64-73.
[6]	JI Chao,WU Luming,LI Bin,ZANG Jiazhong,YU Haibin. Research progress on modification of SAPO-34 as catalyst for methanol to olefins [J]. Inorganic Chemicals Industry, 2022, 54(7): 1-9.
[7]	Peng Xiaowei,Wang Yinbin,Zang Jiazhong,Yu Haibin. Research on preparation of metal modified catalysts and catalytic performances of methanol aromatization [J]. Inorganic Chemicals Industry, 2021, 53(9): 104-108.
[8]	Xiao Yihan,Cao Jianxin,Liu Fei,Yi Yun. Effect of calcination temperature on physicochemical properties and catalytic performance of MnZnO_x [J]. Inorganic Chemicals Industry, 2021, 53(4): 95-100.
[9]	Li Xiaoguo,Li Yongheng,Hou Zhanggui,Han Guodong,Xiao Jiawang,Gao Jinping,Chang Yang. Study on pilot catalytic performance of the modified catalyst for alkylation of toluene with methanol to p-xylene [J]. Inorganic Chemicals Industry, 2021, 53(3): 97-101.
[10]	Hou Zhanggui,Zhu Qianqian,Li Xiaoguo,Li Yongheng,Chang Yang,Zhang Anfeng,Guo Xinwen. Preparation of modificated micro-mesoporous ZSM-5 molecular sieve catalyst and its catalytic performance for alkylation of toluene with methanol [J]. Inorganic Chemicals Industry, 2020, 52(9): 96-99.
[11]	Li Xiangguo,Guo Miao,Yao Huimin,Lü Jing. Research on hydrothermal synthesis and photoluminescence mechanism of rhombus CeO₂ [J]. Inorganic Chemicals Industry, 2020, 52(6): 30-35.
[12]	Su Wei,Zhang Linfeng,Lü Qingyang,Xia Yuyan,Yuan Hua. Synthesis of diphenyl carbonate by oxidative carbonylation over palladium loaded MnO_x-based bimetallic oxide catalysis [J]. Inorganic Chemicals Industry, 2019, 51(9): 91-96.
[13]	Liu Zhikai1，Cao Hui2，Wang Tianyun1，Han Guodong2，Liu Yi1，Zhang Yi1. Study on novel catalysts for direct catalytic conversion of unconventional natural gas to aromatics [J]. Inorganic Chemicals Industry, 2019, 51(12): 83-88.
[14]	Li Shuwen，Zhou Yan，Wang Tielin. Study on preparation and photocatalysis reduction for CO2 of BiVO4/rGO composite [J]. Inorganic Chemicals Industry, 2019, 51(11): 82-87.
[15]	SHI Guo-Jun, XU 二Gang, CHEN Bin-Bin, SHEN Jian-Yi. Synthesis of hexagonal MoO3 catalysts for selective oxidation of methanol to formaldehyde [J]. INORGANICCHEMICALSINDUSTRY, 2016, 48(3): 77-.

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Study on preparation and catalytic performance of ZnO-CeO₂

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