Effect of Ce modification on the performance of CuLDH catalyst for CO<sub>2</sub> hydrogenation to methanol

LIU Haoran; YU Zhiqing; HUANG Wenbin; WEI Qiang; JIANG Peng; ZHOU Yasong

doi:10.1016/S1872-5813(23)60392-5

Volume 52 Issue 2

Feb. 2024

Turn off MathJax

Article Contents

Article Navigation > Journal of Fuel Chemistry and Technology > 2024 > 52(2): 159-170

LIU Haoran, YU Zhiqing, HUANG Wenbin, WEI Qiang, JIANG Peng, ZHOU Yasong. Effect of Ce modification on the performance of CuLDH catalyst for CO2 hydrogenation to methanol[J]. Journal of Fuel Chemistry and Technology, 2024, 52(2): 159-170. doi: 10.1016/S1872-5813(23)60392-5

Citation:

LIU Haoran, YU Zhiqing, HUANG Wenbin, WEI Qiang, JIANG Peng, ZHOU Yasong. Effect of Ce modification on the performance of CuLDH catalyst for CO₂ hydrogenation to methanol[J]. Journal of Fuel Chemistry and Technology, 2024, 52(2): 159-170. doi: 10.1016/S1872-5813(23)60392-5

Citation:

PDF( 8608 KB)

Effect of Ce modification on the performance of CuLDH catalyst for CO₂ hydrogenation to methanol

doi: 10.1016/S1872-5813(23)60392-5

LIU Haoran^1
,,
YU Zhiqing^1
,,
HUANG Wenbin^1
,,
WEI Qiang^1
,,
JIANG Peng^2
,,
ZHOU Yasong^{1
,
,}

1.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China
2.
CNPC Kunlun Capital Co., Ltd, Haikou 571127, China

Funds: The project was supported by National Natural Science Foundation of China (22078360).

Received Date: 2023-08-18
Accepted Date: 2023-09-21
Rev Recd Date: 2023-09-21

Available Online: 2023-11-10

Publish Date: 2024-02-02

Abstract

Abstract

A series of Ce modified CuLDH-Cex catalysts were synthesized by adding different amounts of Ce to CuMgAl hydrotalcite (CuLDH) catalysts. The physicochemical properties of the catalysts were characterized by X-ray diffraction (XRD), N₂ adsorption-desorption (BET), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), etc. The results showed that the addition of Ce changed the hydrotalcite structure of CuLDH catalyst, and an appropriate amount of Ce increased the surface area of the catalyst and improved the dispersion of Cu particles. At the same time, an appropriate amount of Ce was beneficial for increasing the density of strong alkaline sites and the number of oxygen vacancies on the catalyst surface, promoting the adsorption and conversion of CO₂. Ce was beneficial for adjusting the Cu⁺/Cu⁰ ratio on the catalyst surface, and a higher Cu⁺/Cu⁰ ratio was conducive to the formation of methanol. When the Ce/Cu ratio was 0.3, the catalyst exhibited higher activity with 7.5% CO₂ conversion, 78.4% methanol selectivity and 362.8 g/(kg·h) spatiotemporal yield at 240 ℃ under 2.5 MPa with a GHSV=9000 mL/(g·h). It was proved by in-situ DRIFTS that CuLDH-Ce0.3 catalyst followed HCOO* reaction path during CO₂ hydrogenation for methanol.
- Ce,
- hydrotalcite,
- CO₂ hydrogenation,
- alkaline sites,
- oxygen vacancies,
- methanol

FullText(HTML)

References(48)

References

[1]	SHA F, HAN Z, TANG S, et al. Hydrogenation of carbon dioxide to methanol over non-Cu-based heterogeneous catalysts[J]. ChemSusChem,2020,13(23):6160−6181. doi: 10.1002/cssc.202002054
[2]	LI S, GUO L, ISHIHARA T. Hydrogenation of CO₂ to methanol over Cu/AlCeO catalyst[J]. Catal Today,2020,339:352−361. doi: 10.1016/j.cattod.2019.01.015
[3]	CHANG K, ZHANG H, CHENG M J, et al. Application of ceria in CO₂ conversion catalysis[J]. ACS Catal,2019,10(1):613−631.
[4]	JIA X, SUN K, WANG J, et al. Selective hydrogenation of CO₂ to methanol over Ni/In₂O₃ catalyst[J]. J Energy Chem,2020,50:409−415. doi: 10.1016/j.jechem.2020.03.083
[5]	TAN Q, SHI Z, WU D. CO₂ hydrogenation to methanol over a highly active Cu-Ni/CeO₂-nanotube catalyst[J]. Ind Eng Chem Res,2018,57(31):10148−10158. doi: 10.1021/acs.iecr.8b01246
[6]	GAO P, ZHANG L N, LI S G, et al. Novel heterogeneous catalysts for CO₂ hydrogenation to liquid fuels[J]. ACS Cent Sci,2020,6(10):1657−1670. doi: 10.1021/acscentsci.0c00976
[7]	ZHAN F, FAN L, XU K, et al. Hierarchical sheet-like Cu/Zn/Al nanocatalysts derived from LDH/MOF composites for CO₂ hydrogenation to methanol[J]. J CO₂ Util,2019,33:222−232. doi: 10.1016/j.jcou.2019.05.021
[8]	LU Z, WANG J, SUN K H, et al. CO₂ hydrogenation to methanol over Rh/In₂O₃-ZrO₂ catalyst with improved activity[J]. Green Chem Eng ,2022,3(2):165−170.
[9]	LI M M J, CHEN C P, AYVALI T, et al. CO₂ Hydrogenation to methanol over catalysts derived from single cationic layer CuZnGa LDH precursors[J]. ACS Catal,2018,8(5):4390−4401. doi: 10.1021/acscatal.8b00474
[10]	SHI Z, TAN Q, WU D. Enhanced CO₂ hydrogenation to methanol over TiO₂ nanotubes-supported CuO-ZnO-CeO₂ catalyst[J]. Appl Catal A: Gen,2019,581:58−66. doi: 10.1016/j.apcata.2019.05.019
[11]	CHENG S Y, KOU J W, GAO Z H, et al. Preparation of complexant-modified Cu/ZnO/Al₂O₃ catalysts via hydrotalcite-like precursors and its highly efficient application in direct synthesis of isobutanol and ethanol from syngas[J]. Appl Catal A: Gen,2018,556:113−220. doi: 10.1016/j.apcata.2018.02.027
[12]	ZHANG F, ZHANG Y L, LIU Y, et al. Synthesis of Cu/Zn/Al/Mg catalysts on methanol production by different precipitation methods[J]. Mol Catal,2017,441:190−198. doi: 10.1016/j.mcat.2017.08.015
[13]	XIAO S, ZHANG Y, GAO P, et al. Highly efficient Cu-based catalysts via hydrotalcite-like precursors for CO₂ hydrogenation to methanol[J]. Catal Today,2017,281:327−36. doi: 10.1016/j.cattod.2016.02.004
[14]	LI S Z, WANG Y, YANG B, et al. A highly active and selective mesostructured Cu/AlCeO catalyst for CO₂ hydrogenation to methanol[J]. Appl Catal A: Gen,2019,571:51−60. doi: 10.1016/j.apcata.2018.12.008
[15]	ZHANG C, YANG H Y, GAO P, et al. Preparation and CO₂ hydrogenation catalytic properties of alumina microsphere supported Cu-based catalyst by deposition-precipitation method[J]. J CO₂ Util,2017,17:263−272. doi: 10.1016/j.jcou.2016.11.015
[16]	OUYANG B, TAN W L, LIU B. Morphology effect of nanostructure ceria on the Cu/CeO₂ catalysts for synthesis of methanol from CO₂ hydrogenation[J]. Catal Commun,2017,95:36−39. doi: 10.1016/j.catcom.2017.03.005
[17]	GAO P, XIE R Y, WANG H, et al. Cu/Zn/Al/Zr catalysts via phase-pure hydrotalcite-like compounds for methanol synthesis from carbon dioxide[J]. J CO₂ Util,2015,11:41−48. doi: 10.1016/j.jcou.2014.12.008
[18]	FANG X, MEN Y H, WU F, et al. Moderate-pressure conversion of H₂ and CO₂ to methanol via adsorption enhanced hydrogenation[J]. Int J Hydrogen Energy,2019,44(39):21913−21925. doi: 10.1016/j.ijhydene.2019.06.176
[19]	GAO P, ZHONG L S, ZHANG L N, et al. Yttrium oxide modified Cu/ZnO/Al₂O₃ catalysts via hydrotalcite-like precursors for CO₂ hydrogenation to methanol[J]. Catal Sci Technol,2015,5(9):4365−4377.
[20]	GAO P, YANG H Y, ZHANG L N, et al. Fluorinated Cu/Zn/Al/Zr hydrotalcites derived nanocatalysts for CO₂ hydrogenation to methanol[J]. J CO₂ Util,2016,16:32−41. doi: 10.1016/j.jcou.2016.06.001
[21]	GAO P, LI F, ZHAO N, et al. Influence of modifier (Mn, La, Ce, Zr and Y) on the performance of Cu/Zn/Al catalysts via hydrotalcite-like precursors for CO₂ hydrogenation to methanol[J]. Appl Catal A: Gen,2013,468:442−452. doi: 10.1016/j.apcata.2013.09.026
[22]	LIM A, YEO J W, ZENG H C. Preparation of CuZn-doped MgAl-layered double hydroxide catalysts through the memory effect of hydrotalcite for effective hydrogenation of CO₂ to Methanol[J]. ACS Appl Energy Mater,2023,6(2):782−794. doi: 10.1021/acsaem.2c03045
[23]	CORED J, MAZARIO J, CERDA-MORENO C, et al. Enhanced methanol production over non-promoted Cu-MgO-Al₂O₃ Materials with ex-solved 2 nm Cu particles: Insights from an operando spectroscopic study[J]. ACS Catal,2022,12(7):3845−3857. doi: 10.1021/acscatal.1c06044
[24]	FANG X, MEN Y H, WU F, et al. Improved methanol yield and selectivity from CO₂ hydrogenation using a novel Cu-ZnO-ZrO₂ catalyst supported on Mg-Al layered double hydroxide (LDH)[J]. J CO₂ Util,2019,29:57−64. doi: 10.1016/j.jcou.2018.11.006
[25]	WANG X, ALABSI M H, ZHENG P, et al. PdCu supported on dendritic mesoporous Ce_xZr_1-xO₂ as superior catalysts to boost CO₂ hydrogenation to methanol[J]. J Colloid Interface Sci,2022,611:739−751. doi: 10.1016/j.jcis.2021.11.172
[26]	YOO C J, LEE D W, KIM M S, et al. The synthesis of methanol from CO/CO₂/H₂ gas over Cu/Ce_1-xZr_xO₂ catalysts[J]. J Mol Catal A: Chem,2013,378:255−262. doi: 10.1016/j.molcata.2013.06.023
[27]	LI N, WANG W W, SONG L X, et al. CO₂ hydrogenation to methanol promoted by Cu and metastable tetragonal Ce_xZr_yO_z interface[J]. J Energy Chem,2022,68:771−779. doi: 10.1016/j.jechem.2021.12.053
[28]	HU X S, ZHAO C Y, GUAN Q X, et al. Selective hydrogenation of CO₂ over a Ce promoted Cu-based catalyst confined by SBA-15[J]. Inorg Chem Front,2019,6(7):1799−1812. doi: 10.1039/C9QI00397E
[29]	WANG W W, QU Z P, SONG L X, et al. CO₂ hydrogenation to methanol over Cu/CeO₂ and Cu/ZrO₂ catalysts: Tuning methanol selectivity via metal-support interaction[J]. J Energy Chem,2020,40:22−30. doi: 10.1016/j.jechem.2019.03.001
[30]	ZHANG J P, SUN X H, WU C Y, et al. Engineering Cu⁺/CeZrO interfaces to promote CO₂ hydrogenation to methanol[J]. J Energy Chem,2023,77:45−53. doi: 10.1016/j.jechem.2022.10.034
[31]	SHAO Y W, WANG J Z, DU H N, et al. Importance of magnesium in Cu-based catalysts for selective conversion of biomass-derived furan compounds to diols[J]. ACS Sustainable Chem Eng,2020,8(13):5217−5228. doi: 10.1021/acssuschemeng.9b07841
[32]	GOSWAMI K, ANANTHAKRISHNAN R. Ce-doped CuMgAl oxide as a redox couple mediated catalyst for visible light aided photooxidation of organic pollutants[J]. ACS Appl Nano Mater,2019,2(9):6030−6039. doi: 10.1021/acsanm.9b01557
[33]	LI D L, CAI Y B, CHEN C Q, et al. Magnesium-aluminum mixed metal oxide supported copper nanoparticles as catalysts for water-gas shift reaction[J]. Fuel,2016,184:382−389. doi: 10.1016/j.fuel.2016.06.131
[34]	ZHU J D, CIOLCA D, LIU L, et al. Flame synthesis of Cu/ZnO-CeO₂ catalysts: Synergistic metal-support interactions promote CH₃OH selectivity in CO₂ hydrogenation[J]. ACS Catal,2021,11(8):4880−4892. doi: 10.1021/acscatal.1c00131
[35]	CHEN G Q, YU J, LI G H, et al. Cu⁺-ZrO₂ interfacial sites with highly dispersed copper nanoparticles derived from Cu@UiO-67 hybrid for efficient CO2 hydrogenation to methanol[J]. Int J Hydrogen Energy,2023,48(7):2605−2616. doi: 10.1016/j.ijhydene.2022.10.172
[36]	NIU J T, LIU H Y, JIN Y, et al. Comprehensive review of Cu-based CO₂ hydrogenation to CH₃OH: Insights from experimental work and theoretical analysis[J]. Int J Hydrogen Energy,2022,47(15):9183−9200. doi: 10.1016/j.ijhydene.2022.01.021
[37]	XU Y N, GAO Z H, PENG L, et al. A highly efficient Cu/ZnO_x/ZrO₂ catalyst for selective CO₂ hydrogenation to methanol[J]. J Catal,2022,414:236−244. doi: 10.1016/j.jcat.2022.09.011
[38]	XU Y M, DING Z L, QIU R, et al. Effect of support and reduction temperature in the hydrogenation of CO₂ over the Cu-Pd bimetallic catalyst with high Cu/Pd ratio[J]. Int J Hydrogen Energy,2022,47(65):27973−27985. doi: 10.1016/j.ijhydene.2022.06.110
[39]	WANG Y D, YU H R, HU Q, et al. Application of microimpinging stream reactor coupled with ultrasound in Cu/CeZrO_x solid solution catalyst preparation for CO₂ hydrogenation to methanol[J]. Renewable Energy,2023,202:834−843. doi: 10.1016/j.renene.2022.11.075
[40]	SUN X C, JIN Y F, CHENG Z Z, et al. Dual active sites over Cu-ZnO-ZrO₂ catalysts for carbon dioxide hydrogenation to methanol[J]. J Environ Sci,2023,131:162−172. doi: 10.1016/j.jes.2022.10.002
[41]	ZHANG C C, WANG L T, ETIM U J, et al. Oxygen vacancies in Cu/TiO₂ boost strong metal-support interaction and CO₂ hydrogenation to methanol[J]. J Catal,2022,413:284−296. doi: 10.1016/j.jcat.2022.06.026
[42]	SHEN C Y, BAO Q Q, XUE W J, et al. Synergistic effect of the metal-support interaction and interfacial oxygen vacancy for CO₂ hydrogenation to methanol over Ni/In₂O₃ catalyst: A theoretical study[J]. J Energy Chem,2022,65:623−629. doi: 10.1016/j.jechem.2021.06.039
[43]	LI J, DU T, LI Y N, et al. Novel layered triple hydroxide sphere CO₂ adsorbent supported copper nanocluster catalyst for efficient methanol synthesis via CO₂ hydrogenation[J]. J Catal,2022,409:24−32. doi: 10.1016/j.jcat.2022.03.020
[44]	GUO T, GUO Q, LI S Z, et al. Effect of surface basicity over the supported Cu-ZnO catalysts on hydrogenation of CO₂ to methanol[J]. J Catal,2022,407:312−321. doi: 10.1016/j.jcat.2022.01.035
[45]	COLLINS S E, BALTANAS M A, DELGDO J J, et al. CO₂ hydrogenation to methanol on Ga₂O₃-Pd/SiO₂ catalysts: Dual oxide-metal sites or (bi)metallic surface sites?[J]. Catal Today,2021,381:154−62. doi: 10.1016/j.cattod.2020.07.048
[46]	SHA F, TANG S, TANG C Z, et al. The role of surface hydroxyls on ZnZrO_x solid solution catalyst in CO₂ hydrogenation to methanol[J]. Chin J Catal,2023,45:162−173. doi: 10.1016/S1872-2067(22)64176-7
[47]	DASIREDDY V D B C, LIKOZAR B. The role of copper oxidation state in Cu/ZnO/Al₂O₃ catalysts in CO₂ hydrogenation and methanol productivity[J]. Renewable Energy,2019,140:452−460. doi: 10.1016/j.renene.2019.03.073
[48]	HAN X Y, LI M S, CHANG X, et al. Hollow structured Cu@ZrO₂ derived from Zr-MOF for selective hydrogenation of CO₂ to methanol[J]. J Energy Chem,2022,71:277−287. doi: 10.1016/j.jechem.2022.03.034