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广西科技大学 生物与化学工程学院,广西 柳州 545000
Received:02 August 2025,
Revised:2025-08-28,
Published:25 June 2026
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杨红丽,常盼盼,董金诗.CeO2暴露晶面对Rh-CeO2催化剂CO2甲烷化催化性能的影响[J].低碳化学与化工,2026,51(6):1-12. DOI: 10.12434/j.issn.2097-2547.20250332.
YANG Hongli,CHANG Panpan,DONG Jinshi.Effects of CeO2 exposed facets on catalytic performances of Rh-CeO2 catalysts for CO2 methanation[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(6):1-12. DOI: 10.12434/j.issn.2097-2547.20250332.
杨红丽,常盼盼,董金诗.CeO2暴露晶面对Rh-CeO2催化剂CO2甲烷化催化性能的影响[J].低碳化学与化工,2026,51(6):1-12. DOI: 10.12434/j.issn.2097-2547.20250332. DOI:
YANG Hongli,CHANG Panpan,DONG Jinshi.Effects of CeO2 exposed facets on catalytic performances of Rh-CeO2 catalysts for CO2 methanation[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(6):1-12. DOI: 10.12434/j.issn.2097-2547.20250332. DOI:
CO
2
甲烷化是实现“碳中和”的重要化学手段之一,然而开发具有高甲烷(CH
4
)选择性的催化剂具有一定挑战。采用煅烧法和水热合成法制备了不同微观形貌的CeO
2
载体,并负载质量分数为0.5%的Rh制备了CeO
2
暴露晶面不同的Rh-CeO
2
催化剂,通过不同表征方法,系统探究了CeO
2
暴露晶面对Rh-CeO
2
催化剂CO
2
甲烷化催化性能的影响。结果显示,0.5Rh-CeO
2
-NC(NC表示纳米立方体)催化性能最优,400 °C时CH
4
选择性高达76%,CH
4
产率为29.19%。CeO
2
(100)晶面在还原预处理后更容易形成表面氧空位,有利于CO
2
活化,并且富电子的Rh单原子聚集成纳米颗粒,加强了H
2
活化,从而促进了CH
4
生成。原位DRIFTS证实Rh-CeO
2
催化剂作用下,CO
2
甲烷化遵循甲酸盐路径与CO路径共存的机制,且两种路径的竞争关系受CeO
2
暴露晶面调控。
CO
2
methanation is one of the important chemical strategies to achieve “carbon neutrality”. However
developing catalysts with high methane (CH
4
)
selectivity remains challenging. CeO
2
supports with different morphologies were prepared via calcination or hydrothermal method
and Rh-CeO
2
catalysts with different exposed facets of CeO
2
were prepared by loading 0.5% (mass fraction) Rh. The effects of the exposed facets of CeO
2
on catalytic performances of Rh-CeO
2
catalysts for CO
2
methanation were systematically investigated. The results show that 0.5Rh-CeO
2
-NC (NC represents nano-cube) exhibits the best catalytic performance with CH
4
selectivity of 76% and CH
4
yield of 29.19% at 400 ℃. The CeO
2
(100) facet facilitates the formation of surface oxygen vacancies after reduction pretreatment
which promotes CO
2
activation
and electron-rich Rh single atoms aggregate into nanoparticles
enhancing H
2
activation and promoting CH
4
formation. In situ DRIFTS confirms that CO
2
methanation with Rh-CeO
2
catalysts follows a dual-path mechanism of formate pathway and CO pathway
and the competition between these two pathways is regulated by CeO
2
exposed facets.
田郡博 , 古芳娜 , 苏发兵 , 等 . 二氧化碳甲烷化催化剂及反应机理研究进展 [J ] . 过程工程学报 , 2023 , 23 ( 3 ): 375 - 395 .
TIAN J B , GU F N , SU F B , et al . CO 2 methanation: Recent advances in catalyst development and reaction mechanistic study [J ] . The Chinese Journal of Process Engineering , 2023 , 23 ( 3 ): 375 - 395 .
KAMKENG A D N , WANG M H , HU J , et al . Transformation technologies for CO 2 utilisation: Current status, challe nges and future prospects [J ] . Chemical Engineering Journal , 2021 , 409 : 128138 .
刘洋 , 田菊梅 , 李海鹏 , 等 . 光热催化CO 2 甲烷化Ni基催化剂研究进展 [J ] . 低碳化学与化工 , 2025 , 50 ( 5 ): 1 - 10 .
LIU Y , TIAN J M , LI H , et al . Research progress on Ni-based catalysts for photothermal catalytic CO 2 methanation [J ] . Low-Carbon Chemistry and Chemical Engineering , 2025 , 50 ( 5 ): 1 - 10 .
SHARMA S , HU Z P , ZHANG P , et al . CO 2 methanation on Ru-doped ceria [J ] . Journal of Catalysis , 2011 , 278 ( 2 ): 297 - 309 .
RUI N , WANG X L , DENG K X , et al . Atomic structural origin of the high methanol selectivity over In 2 O 3 -metal interfaces: Metal-support interactions and the formation of a InO x overlayer in Ru/In 2 O 3 catalysts during CO 2 hydrogenation [J ] . ACS Catalysis , 2023 , 13 ( 5 ): 3187 - 3200 .
WANG F , HE S , CHEN H , et al . Active site dependent reaction mechanism over Ru/CeO 2 catalyst toward CO 2 methanation [J ] . Journal of the American Chemical Society , 2016 , 138 ( 19 ): 6298 - 6305 .
ZHAO Z W , ZHOU X , LIU Y N , et al . Ultrasmall Ni nanoparticles embedded in Zr-based MOFs provide high selectivity for CO 2 hydrogenation to methane at low temperatures [J ] . Catalysis Science & Technology , 2018 , 8 ( 12 ): 3160 - 3165 .
DU Y X , QIN C , XU Y F , et al . Ni nanoparticles dispersed on oxygen vacancies-rich CeO 2 nanoplates for enhanced low-temperature CO 2 methanation performance [J ] . Chemical Engineering Journal , 2021 , 418 : 129402 .
SIANG T J , JALIL A A , FATAH N A A , et al . Tailoring Rh content on dendritic fibrous silica alumina catalyst for enhanced CO 2 capture in catalytic CO 2 methanation [J ] . Journal of Environmental Chemical Engineering , 2021 , 9 ( 1 ): 104616 .
ITALIANO C , DRAGO FERRANTE G , PINO L , et al . Silicon carbide and alumina open-cell foams activated by Ni/CeO 2 -ZrO 2 catalyst for CO 2 methanation in a heat-exchanger reactor [J ] . Chemical Engineering Journal , 2022 , 434 : 134685 .
HE C X , LI Q X , YE Z C , et al . Regulating atomically-precise Pt sites for boosting light-driven dry reforming of methane [J ] . Angewandte Chemie International Edition , 2024 , 63 ( 46 ): e202412308 .
李妮娜 , 李正甲 , 岑洁 , 等 . 低温CO 2 甲烷化催化剂研究进展 [J ] . 高校化学工程学报 , 2026 , 40 ( 1 ): 1 - 9 .
LI N N , LI Z J , CEN J , et al . Research process on low-temperature CO 2 methanation catalysts [J ] . Journal of Chemical Engineering of Chinese Universities , 2026 , 40 ( 1 ): 1 - 9 .
MATSUBU J C , ZHANG S , DERITA L , et al . Adsorbate-mediated strong metal-support interactions in oxide-supported Rh catalysts [J ] . Nature Chemistry , 2016 , 9 ( 2 ): 120 - 127 .
ARANDIYAN H , WANG Y , SCOTT J , et al . In situ exsolution of bimetallic Rh-Ni nanoalloys: A highly efficient catalyst for CO 2 methanation [J ] . ACS Applied Materials & Interfaces , 2018 , 10 ( 19 ): 16352 - 16357 .
WANG F , LI C M , ZHANG X Y , et al . Catalytic behavior of supported Ru nanoparticles on the {100}, {110}, and {111} facet of CeO 2 [J ] . Journal of Catalysis , 2015 , 329 : 177 - 186 .
MATSUBU J C , YANG V N , CHRISTOPHER P . Isolated metal active site concentration and stability control catalytic CO 2 reduction selectivity [J ] . Journal of the American Chemical Society , 2015 , 137 ( 8 ): 3076 - 3084 .
LI S , XU Y X , WANG H W , et al . Tuning the CO 2 hydrogenation selectivity of rhodium single-atom catalysts on zirconium dioxide with zlkali ions [J ] . Angewandte Chemie International Edition , 2023 , 62 ( 8 ): e202218167 .
MARTIN N M , VELIN P , SKOGLUNDH M , et al . Catalytic hydrogenation of CO 2 to methane over supported Pd, Rh and Ni catalysts [J ] . Catalysis Science & Technology , 2017 , 7 ( 5 ): 1086 - 1094 .
KARELOVIC A , RUIZ P . CO 2 hydrogenation at low temperature over Rh/ γ -Al 2 O 3 catalysts: Effect of the metal particle size on catalytic performances and reaction mechanism [J ] . Applied Catalysis B: Environmental , 2012 , 113/114 : 237 - 249 .
KARELOVIC A , RUIZ P . Mechanistic study of low temperature CO 2 methanation over Rh/TiO 2 catalysts [J ] . Journal of Catalysis , 2013 , 301 : 141 - 153 .
XIE Z H , HWANG S , CHEN J G . Reduction-induced metal/oxide interfacial sites for selective CO 2 hydrogenation [J ] . SmartMat , 2023 , 4 ( 4 ): e1201 .
SMITH L R , SAINNA M A , DOUTHWAITE M , et al . Gas phase glycerol valorization over ceria nanostructures with well-defined morphologies [J ] . ACS Catalysis , 2021 , 11 ( 8 ): 4893 - 4907 .
MAI H X , SUN L D , ZHANG Y W , et al . Shape-selective synthesis and oxygen storage behavior of ceria nanopolyhedra, nanorods, and nanocubes [J ] . The Journal of Physical Chemistry B , 2005 , 109 ( 51 ): 24380 - 24385 .
DONG J S , LI D K , ZHANG Y T , et al . Insights into the CeO 2 facet-depended performance of propane oxidation over Pt-CeO 2 catalysts [J ] . Journal of Catalysis , 2022 , 407 : 174 - 185 .
莫胜鹏 , 赵心 , 李兵 , 等 . CeO 2 不同形貌对Ru/CeO 2 催化剂结构特性和光热催化CO 2 甲烷化影响研究 [J ] . 中国稀土学报 , 2025 , 43 ( 6 ): 1199 - 1206 .
MO S P , ZHAO X , LI B , et al . Effect of different CeO 2 morphologies on the structural characteristics and photothermal CO 2 methanation of Ru/CeO 2 catalysts [J ] . Journal of the Chinese Society of Rare Earths , 2025 , 43 ( 6 ): 1199 - 1206 .
KWON Y , KIM T Y , KWON G , et al . Selective activation of methane on single-atom catalyst of rhodium dispersed on zirconia for direct conversion [J ] . Journal of the American Chemical Society , 2017 , 139 ( 48 ): 17694 - 17699 .
WU D F , LIU S X , ZHONG M Q , et al . Nature and dynamic evolution of Rh single atoms trapped by CeO 2 in CO hydrogenation [J ] . ACS Catalysis , 2022 , 12 ( 19 ): 12253 - 12267 .
CAI W J , WANG F G , VAN VEEN A C , et al . Autothermal reforming of ethanol for hydrogen production over an Rh/CeO 2 catalyst [J ] . Catalysis Today , 2008 , 138 ( 3/4 ): 152 - 156 .
PINTAR A , BATISTA J , HOČEVAR S . TPR, TPO, and TPD examinations of Cu 0.15 Ce 0.85 O (2- y ) mixed oxides prepared by co-precipitation, by the sol-gel peroxide route, and by citric acid-assisted synthesis [J ] . Journal of Colloid and Interface Science , 2005 , 285 ( 1 ): 218 - 231 .
WANG L B , LI H L , ZHANG W B , et al . Supported rhodium catalysts for ammonia-borane hydrolysis: Dependence of the catalytic activity on the highest occupied state of the single rhodium atoms [J ] . Angewandte Chemie International Edition , 2017 , 56 ( 17 ): 4712 - 4718 .
WANG R , XU H Y , LIU X B , et al . Role of redox couples of Rh 0 /Rh δ + and Ce 4+ /Ce 3+ in CH 4 /CO 2 reforming over Rh-CeO 2 /Al 2 O 3 catalyst [J ] . Applied Catalysis A: General , 2006 , 305 ( 2 ): 204 - 210 .
JACQUEMIN M , BEULS A , RUIZ P . Catalytic production of methane from CO 2 and H 2 at low temperature: Insight on the reaction mechanism [J ] . Catalysis Today , 2010 , 157 ( 1/2/3/4 ): 462 - 466 .
BEULS A , SWALUS C , JACQUEMIN M , et al . Methanation of CO 2 : Further insight into the mechanism over Rh/ γ -Al 2 O 3 catalyst [J ] . Applied Catalysis B: Environmental , 2012 , 113/114 : 2 - 10 .
DONG J S , YANG H L , LI S T , et al . Insights into Rh size-dependent reactivity of CO 2 methanation over Rh-Al 2 O 3 catalysts [J ] . RSC Advances , 2025 , 15 ( 30 ): 24930 - 24941 .
ZHENG H , LIAO W Q , DING J Q , et al . Unveiling the key factors in determining the activity and selectivity of CO 2 hydrogenation over Ni/CeO 2 catalysts [J ] . ACS Catalysis , 2022 , 12 ( 24 ): 15451 - 15462 .
ZHOU G , LIU H , CUI K , et al . Role of surface Ni and Ce species of Ni/CeO 2 catalyst in CO 2 methanation [J ] . Applied Surface Science , 2016 , 383 : 248 - 252 .
MI R L , LI D , HU Z , et al . Morphology effects of CeO 2 nanomaterials on the catalytic combustion of toluene: A combined kinetics and diffuse reflectance infrared fourier transform spectroscopy study [J ] . ACS Catalysis , 2021 , 11 ( 13 ): 7876 - 7889 .
HOLMGREN A , ANDERSSON B , DUPREZ D . Interactions of CO with Pt/ceria catalysts [J ] . Applied Catalysis B: Environmental , 1999 , 22 ( 3 ): 215 - 230 .
CÁRDENAS-ARENAS A , QUINDIMIL A , DAVÓ-QUIÑONERO A , et al . Isotopic and in situ DRIFTS study of the CO 2 methanation mechanism using Ni/CeO 2 and Ni/Al 2 O 3 catalysts [J ] . Applied Catalysis B: Environmental , 2020 , 265 : 118538 .
TANG Y X , ZHAO T T , HAN H C , et al . Ir-CoO active centers supported on porous Al 2 O 3 nanosheets as efficient and durable photo‐thermal catalysts for CO 2 conversion [J ] . Advanced Science , 2023 , 10 ( 15 ): 2300122 .
GUO Y , MEI S , YUAN K , et al . Low-temperature CO 2 methanation over CeO 2 -supported Ru single atoms, nanoclusters, and nanoparticles competitively tuned by strong metal-support interactions and H-spillover effect [J ] . ACS Catalysis , 2018 , 8 ( 7 ): 6203 - 6215 .
ASHOK J , PATI S , HONGMANOROM P , et al . A review of recent catalyst advances in CO 2 methanation processes [J ] . Catalysis Today , 2020 , 356 : 471 - 489 .
YANG B , WANG Y F , GAO B , et al . Size-dependent active site and its catalytic mechanism for CO 2 hydrogenation reactivity and selectivity over Re/TiO 2 [J ] . ACS Catalysis , 2023 , 13 ( 15 ): 10364 - 10374 .
WANG Y , LI L , LI G Y , et al . Synergy of oxygen vacancies and Ni 0 species to promote the stability o f a Ni/ZrO 2 catalyst for dry reforming of methane at low temperatures [J ] . ACS Catalysis , 2023 , 13 ( 10 ): 6486 - 6496 .
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