LaCuZnX (X=Al, Zr, Al+Zr) perovskite-like catalysts treated by NaBH4 and their catalytic performance for CO2 hydrogenation to methanol

KUANG Zhi-qi; LI Feng; LUO Jing; WANG Yan-xia; YUAN Dan-ping; WANG Qin; ZHAO Hai-hong; WANG Shi-wei; ZHAO Ning; XIAO Fu-kui

Volume 48 Issue 3

Mar. 2020

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Article Navigation > Journal of Fuel Chemistry and Technology > 2020 > 48(3): 293-301

KUANG Zhi-qi, LI Feng, LUO Jing, WANG Yan-xia, YUAN Dan-ping, WANG Qin, ZHAO Hai-hong, WANG Shi-wei, ZHAO Ning, XIAO Fu-kui. LaCuZnX (X=Al, Zr, Al+Zr) perovskite-like catalysts treated by NaBH4 and their catalytic performance for CO2 hydrogenation to methanol[J]. Journal of Fuel Chemistry and Technology, 2020, 48(3): 293-301.

Citation:

KUANG Zhi-qi, LI Feng, LUO Jing, WANG Yan-xia, YUAN Dan-ping, WANG Qin, ZHAO Hai-hong, WANG Shi-wei, ZHAO Ning, XIAO Fu-kui. LaCuZnX (X=Al, Zr, Al+Zr) perovskite-like catalysts treated by NaBH₄ and their catalytic performance for CO₂ hydrogenation to methanol[J]. Journal of Fuel Chemistry and Technology, 2020, 48(3): 293-301.

Citation:

KUANG Zhi-qi, LI Feng, LUO Jing, WANG Yan-xia, YUAN Dan-ping, WANG Qin, ZHAO Hai-hong, WANG Shi-wei, ZHAO Ning, XIAO Fu-kui. LaCuZnX (X=Al, Zr, Al+Zr) perovskite-like catalysts treated by NaBH₄ and their catalytic performance for CO₂ hydrogenation to methanol[J]. Journal of Fuel Chemistry and Technology, 2020, 48(3): 293-301.

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LaCuZnX (X=Al, Zr, Al+Zr) perovskite-like catalysts treated by NaBH₄ and their catalytic performance for CO₂ hydrogenation to methanol

KUANG Zhi-qi^{1, 2},
LI Feng^{1
,
,},
LUO Jing^{1, 2},
WANG Yan-xia^{1, 2},
YUAN Dan-ping^{1, 2},
WANG Qin^{1, 2},
ZHAO Hai-hong^{1, 2},
WANG Shi-wei^{1, 2},
ZHAO Ning¹,
XIAO Fu-kui^{1
,
,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds:

The project was supported by the National Youth Science Foundation of China 21802158

the National Natural Science Foundation of China 21776294

Natural Science Foundation of Shanxi Province 201801D121070

Youth Science Foundation of Shanxi Province 201701D221052

More Information

Corresponding author: LI Feng, E-mail: lifeng2729@sxicc.ac.cn; XIAO Fu-kui, E-mail: xiaofk@sxicc.ac.cn
Received Date: 2019-12-06
Rev Recd Date: 2020-01-09

Available Online: 2021-01-23

Publish Date: 2020-03-10

Abstract

Abstract

La:Cu:Zn:X (X=Zr, Al, Al+Zr) perovskite-like catalysts were prepared by coprecipitation method followed by liquid phase reduction by NaBH₄. The physicochemical properties of the catalysts were tested by a series of characterization methods, and the catalysts were tested for methanol synthesis from CO₂ hydrogenation in a fixed-bed reactor. The results showed that the as-prepared catalysts were mainly composed of La₂CuO₄ perovskite-like crystal structure and doping of elements led to the spatial distortion of the perovskite-like structure. After reduction by NaBH₄, metal copper species and some high-valence copper species were found, which could be further reduced during the reaction. The CO₂ conversion was positively correlated with the Cu surface area, the dispersion of Cu, and the (Cu^α++Cu⁰)/Cu_total of the catalyst. The higher methanol selectivity was obtained when Cu^α+ binding energy was farther away from Cu⁺ binding energy. LCZA had the highest CO₂ conversion, LCZ catalyst possessed the highest methanol selectivity, and LCZZA catalyst presented the optimal methanol space time yield.
- CO₂ hydrogenation,
- methanol,
- perovskite-like,
- liquid reduction method

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References(39)

References

[1]	CHOUDHURY J. New strategies for CO₂-to-methanol conversion[J]. ChemCatChem, 2012, 4(5):609-611. doi: 10.1002/cctc.201100495
[2]	OLAH G A. Beyond oil and gas:The methanol economy[J]. Angew Chem Int Ed, 2005, 44(18):2636-2639. doi: 10.1002/anie.200462121
[3]	DU X L, JIANG Z, SU D S, WANG J Q. Research progress on the indirect hydrogenation of carbon dioxide to methanol[J]. ChemSusChem, 2016, 9(4):322-332. doi: 10.1002/cssc.201501013
[4]	SLOCZYNSKI J, GRABOWSKI R, KOZLOWSKA A, OLSZEWSKI P, STOCH J, SKRZYPEK J, LACHOWSKA M. Catalytic activity of the M/(3ZnO center dot ZrO₂) system (M=Cu, Ag, Au) in the hydrogenation of CO₂ to methanol[J]. Appl Catal A:Gen, 2004, 278(1):11-23. doi: 10.1016/j.apcata.2004.09.014
[5]	KATTEL S, YAN B, YANG Y, CHEN J G, LIU P. Optimizing binding energies of key intermediates for CO₂ hydrogenation to methanol over oxide-supported copper[J]. J Am Chem Soc, 2016, 138(38):12440-12450. doi: 10.1021/jacs.6b05791
[6]	GUO X, MAO D, LU G, WANG S, WU G. The influence of La doping on the catalytic behavior of Cu/ZrO₂ for methanol synthesis from CO₂ hydrogenation[J]. J Mol Catal A:Chem, 2011, 345(1/2):60-68. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=e78981eb9f339ada505c245ba0c19971
[7]	ZHANG Y L, SUN Q, DENG J F, WU D, CHEN S Y. A high activity Cu/ZnO/Al₂O₃ catalyst for methanol synthesis:Preparation and catalytic properties[J]. Appl Catal A:Gen, 1997, 158(1/2):105-120. doi: 10.1016/S0926-860X(96)00362-6
[8]	DENG J F, SUN Q, ZHANG Y L, CHEN S Y, WU D. A novel process for preparation of a Cu/ZnO/Al₂O₃ ultrafine catalyst for methanol synthesis from CO₂+H₂:Comparison of various preparation methods[J]. Appl Catal A:Gen, 1996, 139(1/2):75-85. https://www.researchgate.net/publication/263380583_Preparation_Structure_and_Performance_of_CuO-ZnO-Al2O3_HZSM-5_Core-Shell_Bifunctional_Catalysts_for_One-Step_Synthesis_of_Dimethyl_Ether_from_CO2H2
[9]	SUN Q, ZHANG Y L, CHEN H Y, DENG J F, WU D, CHEN S Y. Novel process for the preparation of Cu/ZnO and Cu/ZnO/Al₂O₃ ultrafine catalyst:Structure, surface properties, and activity for methanol synthesis from CO₂+H₂[J]. J Catal, 1997, 167(1):92-105. doi: 10.1006/jcat.1997.1554
[10]	WANG D, TAO F, ZHAO H, SONG H, CHOU L. Preparation of Cu/ZnO/Al₂O₃ catalyst for CO₂ hydrogenation to methanol by CO₂ assisted aging[J]. Chin J Catal, 2011, 32(9):1452-1456. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=cuihuaxb201109003
[11]	CHEN C S, WU J H, LAI T W. Carbon dioxide hydrogenation on Cu nanoparticles[J]. J Phys Chem C, 2010, 114(35):15021-15028. doi: 10.1021/jp104890c
[12]	FISHER I A, BELL A T. In situ infrared study of methanol synthesis from H₂/CO over Cu/SiO₂ and Cu/ZrO₂/SiO₂[J]. J Catal, 1998, 178(1):153-173. doi: 10.1006/jcat.1998.2134
[13]	WANG Z Q, XU Z N, ZHANG M J, CHEN Q S, CHEN Y, GUO G C. Insight into composition evolution in the synthesis of high-performance Cu/SiO₂ catalysts for CO₂ hydrogenation[J]. Rsc Adv, 2016, 6(30):25185-25190. doi: 10.1039/C6RA02929A
[14]	GRABOWSKA E. Selected perovskite oxides:Characterization, preparation and photocatalytic properties-A review[J]. Appl Catal B:Environ, 2016, 186:97-126. doi: 10.1016/j.apcatb.2015.12.035
[15]	ZHAN H, LI F, GAO P, ZHAO N, XIAO F, WEI W, SUN Y. Influence of element doping on La-Mn-Cu-O based perovskite precursors for methanol synthesis from CO₂/H₂[J]. Rsc Adv, 2014, 4(90):48888-48896. doi: 10.1039/C4RA07692C
[16]	ZHAN H, LI F, XIN C, ZHAO N, XIAO F, WEI W, SUN Y. Performance of the La-Mn-Zn-Cu-O based perovskite precursors for methanol synthesis from CO₂ hydrogenation[J]. Catal Lett, 2015, 145(5):1177-1185. doi: 10.1007/s10562-015-1513-8
[17]	BELIN S, BRACEY C L, BRIOIS V, ELLIS P R, HUTCHINGS G J, HYDE T I, SANKAR G. CuAu/SiO₂ catalysts for the selective oxidation of propene to acrolein:The impact of catalyst preparation variables on material structure and catalytic performance[J]. Catal Sci Technol, 2013, 3(11):2944-2957. doi: 10.1039/c3cy00254c
[18]	CHEN L C, LIN S D. The ethanol steam reforming over Cu-Ni/SiO₂ catalysts:Effect of Cu/Ni ratio[J]. Appl Catal B:Environ, 2011, 106(3/4):639-649. https://www.sciencedirect.com/science/article/abs/pii/S0926337311003043
[19]	LIAW B J, CHEN Y Z. Catalysis of ultrafine CuB catalyst for hydrogenation of olefinic and carbonyl groups[J]. Appl Catal A:Gen, 2000, 196(2):199-207. doi: 10.1016/S0926-860X(99)00464-0
[20]	YUAN Z, WANG L, WANG J, XIA S, CHEN P, HOU Z, ZHENG X. Hydrogenolysis of glycerol over homogenously dispersed copper on solid base catalysts[J]. Appl Catal B:Environ, 2011, 101(3/4):431-440. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=94e7f00688faea6c205fb8e769aebb9e
[21]	YANG R, YU X, ZHANG Y, LI W, TSUBAKI N. A new method of low-temperature methanol synthesis on Cu/ZnO/Al₂O₃ catalysts from CO/CO₂/H₂[J]. Fuel, 2008, 87(4/5):443-450. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=6cc8ee0616e4d8d4eaa6dd5c21587fba
[22]	POKROVSKI K A, RHODES M D, BELL A T. Effects of cerium incorporation into zirconia on the activity of Cu/ZrO₂ for methanol synthesis via CO hydrogenation[J]. J Catal, 2005, 235(2):368-377. doi: 10.1016/j.jcat.2005.09.002
[23]	MESHKINI F, TAGHIZADEH M, BAHMANI M. Investigating the effect of metal oxide additives on the properties of Cu/ZnO/Al₂O₃ catalysts in methanol synthesis from syngas using factorial experimental design[J]. Fuel, 2010, 89(1):170-175. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=c93bfb0181a6d18c15ee98f92af9ea20
[24]	MALUF S S, NASCENTE P A P, AFONSO C R M, ASSAF E M. Study of La_2-xCa_xCuO₄ perovskites for the low temperature water gas shift reaction[J]. Appl Catal A:Gen, 2012, 413:85-93. doi: 10.1016/j.apcata.2011.10.047
[25]	KARELOVIC A, BARGIBANT A, FERNANDEZ C, RUIZ P. Effect of the structural and morphological properties of Cu/ZnO catalysts prepared by citrate method on their activity toward methanol synthesis from CO₂ and H₂ under mild reaction conditions[J]. Catal Today, 2012, 197(1):109-118. doi: 10.1016/j.cattod.2012.07.029
[26]	GAO P, LI F, XIAO F, ZHAO N, SUN N, WEI W, ZHONG L, SUN Y. Preparation and activity of Cu/Zn/Al/Zr catalysts via hydrotalcite-containing precursors for methanol synthesis from CO₂ hydrogenation[J]. Catal Sci Technol, 2012, 2(7):1447-1454. doi: 10.1039/c2cy00481j
[27]	ZHAN H, LI F, GAO P, ZHAO N, XIAO F, WEI W, ZHONG L, SUN Y. Methanol synthesis from CO₂ hydrogenation over La-M-Cu-Zn-O (M=Y, Ce, Mg, Zr) catalysts derived from perovskite-type precursors[J]. J Power Sources, 2014, 251:113-121. doi: 10.1016/j.jpowsour.2013.11.037
[28]	ARENA F, ITALIANO G, BARBERA K, BORDIGA S, BONURA G, SPADARO L, FRUSTERI F. Solid-state interactions, adsorption sites and functionality of Cu-ZnO/ZrO₂ catalysts in the CO₂ hydrogenation to CH₃OH[J]. Appl Catal A:Gen, 2008, 350(1):16-23. doi: 10.1016/j.apcata.2008.07.028
[29]	ARENA F, ITALIANO G, BARBERA K, BONURA G, SPADARO L, FRUSTERI F. Basic evidences for methanol-synthesis catalyst design[J]. Catal Today, 2009, 143(1/2):80-85. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=b686cb9ab074c2239dca91be205589d9
[30]	ZHU Y F, TAN R Q, YI T, GAO S, YAN C H, CAO L L. Preparation of nanosized La₂CuO₄ perovskite oxide using an amorphous heteronuclear complex as a precursor at low-temperature[J]. J Alloys Compd, 2000, 311(1):16-21. doi: 10.1016/S0925-8388(00)00851-3
[31]	KUMAR B V, VELCHURI R, PRASAD G, SREEDHAR B, RAVIKUMAR K, VITHAL, M. Preparation, characterization, photoactivity and XPS studies of Ln₍₂₎ZrTiO₍₇₎ (Ln=Sm and Nd)[J]. Ceram Int, 2010, 36(4):1347-1355. doi: 10.1016/j.ceramint.2010.01.019
[32]	The U S. Secretary of Commerce on behalf of the United States of America. NIST X-ray Photoelectron Spectroscopy Database[DB/OL].https: //srdata.nist.gov/xps/Default.aspx, 2000-06-06/2019-12-01.
[33]	GAO P, LI F, ZHAN H, ZHAO N, XIAO F, WEI W, ZHONG L, WANG H, SUN Y. Influence of Zr on the performance of Cu/Zn/Al/Zr catalysts via hydrotalcite-like precursors for CO₂ hydrogenation to methanol[J]. J Catal, 2013, 298:51-60. doi: 10.1016/j.jcat.2012.10.030
[34]	WU G, WANG X, WEI W, SUN Y. Fluorine-modified Mg-Al mixed oxides:A solid base with variable basic sites and tunable basicity[J]. Appl Catal A:Gen, 2010, 377(1/2):107-113. doi: 10.1016/j.apcata.2010.01.023
[35]	LIU Y, SUN K, MA H, XU X, WANG X. Cr, Zr-incorporated hydrotalcites and their application in the synthesis of isophorone[J]. Catal Commun, 2010, 11(10):880-883. doi: 10.1016/j.catcom.2010.03.014
[36]	ARENA F, MEZZATESTA G, ZAFARANA G, TRUNFIO G, FRUSTERI F, SPADARO L. Effects of oxide carriers on surface functionality and process performance of the Cu-ZnO system in the synthesis of methanol via CO₂ hydrogenation[J]. J Catal, 2013, 300:141-151. doi: 10.1016/j.jcat.2012.12.019
[37]	WAUGH K C. The absorption and locking-in of hydrogen in copper[J]. Solid State Ionics, 2004, 168(3/4):327-342. doi: 10.1016/j.ssi.2003.05.001
[38]	DONG X, LI F, ZHAO N, XIAO F, WANG J, TAN Y. CO₂ hydrogenation to methanol over Cu/ZnO/ZrO₂ catalysts prepared by precipitation-reduction method[J]. Appl Catal B:Environ, 2016, 191:8-17. doi: 10.1016/j.apcatb.2016.03.014
[39]	GAO P, LI F, ZHAO N, XIAO F, WEI W, ZHONG L, SUN Y. 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