Cu-Zr复合氧化物催化耦合甘油和CO<sub>2</sub>合成碳酸甘油酯

徐换换; 柯义虎

doi:10.1016/S1872-5813(23)60384-6

Cu-Zr复合氧化物催化耦合甘油和CO₂合成碳酸甘油酯

doi: 10.1016/S1872-5813(23)60384-6

徐换换^{1, 2,},
柯义虎^{1, 2, ,}

1.
北方民族大学国家民委化工技术基础重点实验室，宁夏银川 750021
2.
北方民族大学宁夏太阳能化学转化技术重点实验室，宁夏银川 750021

基金项目: 国家自然科学基金 (21862001)，宁夏餐厨废油资源化利用技术研发创新团队(2022QCXTD03)和宁夏低品质资源高值化利用技术研发人才小高地资助

详细信息

通讯作者:
Tel: 13895397566, E-mail: keyihu123@nmu.edu.cn

中图分类号: O643.36
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出版历程
- 收稿日期: 2023-08-08
- 修回日期: 2023-09-04
- 录用日期: 2023-09-05
- 网络出版日期: 2023-10-12
- 刊出日期: 2024-02-02

Synthesis of glycerol carbonate from glycerol and CO₂ over Cu-Zr complex oxide

XU Huanhuan^{1, 2
,},
KE Yihu^{1, 2
, ,}

1.
Key Laboratory of Chemical Engineering and Technology, State Ethnic Affairs Commission, North Minzu University, Yinchuan, 750021, China
2.
Ningxia Key Laboratory of Solar Chemical Conversion Technology, North Minzu University, Yinchuan 750021, China

Funds: The project was supported by National Natural Science Foundation of China (21862001), the Innovative Team for Transforming Waste Cooking Oil into Clean Energy and High Value-Added Chemicals (2022QCXTD03) and the Ningxia Low-Grade Resource High Value Utilization and Environmental Chemical Integration Technology Innovation Team Project, China.

摘要

摘要: 采用水热法合成了一系列不同Cu-Zr物质的量比的Cu_1−xZr_xO₂双金属氧化物，以此为催化剂，将生物柴油生产过程副产物甘油与温室气体CO₂耦合反应制备精细化工产品碳酸甘油酯。结果表明，Zr掺杂量不同，催化剂对甘油羰基化反应效果呈现明显差距，最佳反应条件下，Cu_0.99Zr_0.01O₂催化剂具有最佳催化性能，甘油转化率和碳酸甘油酯选择性分别达到64.1%和85.9%。并且发现与纯CuO和纯ZrO₂相比，Cu_1−xZr_xO₂复合氧化物在甘油与CO₂耦合反应体系中表现出更强的催化活性，结合X射线粉末衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）、N₂吸附-脱附、程序升温还原（H₂-TPR）、程序升温脱附（TPD）、傅里叶变换红外光谱（FT-IR）等表征手段，推测高活性与Zr在CuO表面的分散程度、催化剂表面氧物种含量及酸碱性位点数量有关。此外，为了研究催化剂的稳定性，以Cu_0.99Zr_0.01O₂催化剂作为基准进行了循环性能测试，结果表明，经过六次循环后，甘油的转化率和碳酸甘油酯的选择性未发生明显变化，说明该催化剂稳定性良好。
- 甘油 /
- 碳酸甘油酯 /
- 二氧化碳 /
- 复合氧化物 /
- 2-氰基吡啶
Abstract: A series of Cu_1−xZr_xO₂ bimetallic oxides with different Cu-Zr molar ratios for glycerol carbonate synthesis from glycerol and CO₂ were prepared by hydrothermal method. The results found that the performance was significantly affected by the Zr doping amounts. Under the optimal reaction conditions, the Cu_0.99Zr_0.01O₂ catalyst had the best catalytic performance. The conversion of glycerol and the selectivity of glycerol carbonate reached 64.1% and 85.9%, respectively. Cu_1−xZr_xO₂ complex oxide exhibited better activity than pure CuO and pure ZrO₂. The structures, morphologies and surface properties of the catalysts were characterized by X-ray powder diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), N₂ adsorption and desorption, Temperature programmed reduction (H₂-TPR), Temperature programmed desorption (TPD) and Fourier Transform Infrared Spectroscopy (FT-IR). It is speculated that the high activity is related to the degree of dispersion of Zr on the surface of CuO, the surface content of oxygen species and the number of acidic-basic sites. In addition, catalytic activity did not change significantly after six cycles, indicating the excellent stability of the catalyst.
- glycerol /
- glycerol carbonate /
- carbon dioxide /
- complex oxide /
- 2-cyanopyridine

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FIG. 2926. FIG. 2926.

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图 1 Cu_1−xZr_xO₂催化剂的XRD谱图

Figure 1 XRD patterns of the Cu_1−xZr_xO₂ catalyst

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图 2 Cu_1−xZr_xO₂催化剂的SEM图像

Figure 2 SEM images of the catalysts ((a) CuO, (b) ZrO₂, (c) Cu_0.99Zr_0.01O₂, (d) Cu_0.95Zr_0.05O₂, (e) Cu_0.75Zr_0.25O₂, (f) Cu_0.60Zr_0.40O₂, (j) Cu_0.40Zr_0.60O₂)

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图 3 Cu_0.99Zr_0.01O₂催化剂（a）、（b）TEM图像、（c）HRTEM图像和（d）SAED图像

Figure 3 (a), (b) TEM, (c) HRTEM images and (d) SAED of Cu_0.99Zr_0.01O₂ catalyst

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图 4 Cu_0.99Zr_0.01O₂催化剂的TEM-Mapping图像

Figure 4 TEM-mapping of the Cu_0.99Zr_0.01O₂ catalyst

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图 5 Cu_1−xZr_xO₂催化剂的XPS谱图

Figure 5 XPS spectra of Cu_1−xZr_xO₂ catalysts ((a) full spectra, (b) Cu 2p, (c) Zr 3d, (d) O 1s)

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图 6 Cu_1−xZr_xO₂催化剂的（a）N₂吸附-脱附和（b）孔径分布

Figure 6 (a) N₂ adsorption-desorption isotherms and (b) pore size distribution of Cu_1−xZr_xO₂ catalysts

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图 7 Cu_1−xZr_xO₂催化剂的H₂-TPR谱图

Figure 7 H₂-TPR profiles of the Cu_1−xZr_xO₂ catalyst

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图 8 Cu_1−xZr_xO₂催化剂的TPD谱图

Figure 8 TPD profiles of the Cu_1−xZr_xO₂ catalyst ((a) NH₃-TPD, (b) CO₂-TPD)

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图 9 Cu_1−xZr_xO₂催化剂的FT-IR谱图

Figure 9 FT-IR spectra of the Cu_1−xZr_xO₂ catalyst

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图 10 反应条件对Cu_0.99Zr_0.01O₂催化剂催化活性的影响

Figure 10 Effect of reaction conditions on the catalytic activity of the Cu_0.99Zr_0.01O₂ catalyst

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图 11 催化剂的重复使用性测试

Figure 11 Reusability of the Cu_0.99Zr_0.01O₂catalyst

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图 12 甘油在催化剂上的羧化作用和2-氰基吡啶的水化作用

Figure 12 Carboxylation of glycerol and CO₂ in the presence of 2-cyanopyridine

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表 1 Cu_1−xZr_xO₂样品表面氧种类含量

Table 1 Surface oxygen species contents of Cu_1−xZr_xO₂ samples

Sample	Surface oxygen species content/%
Sample	O_Ⅰ	O_Ⅱ	O_Ⅲ	O_Ⅰ/(O_Ⅱ+O_Ⅲ)
CuO	53.64	33.03	13.33	1.16
Cu_0.99Zr_0.01O₂	57.78	29.85	12.36	1.37
Cu_0.95Zr_0.05O₂	54.9	30.14	14.90	1.22
Cu_0.75Zr_0.25O₂	47.01	43.06	9.93	0.89
Cu_0.60Zr_0.40O₂	34.78	38.91	26.31	0.53
Cu_0.40Zr_0.60O₂	64.60	26.92	8.48	1.82
ZrO₂	74.74	15.05	10.22	2.96

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表 2 Cu_1−xZr_xO₂催化剂的织构性质

Table 2 Texture properties of the Cu_1−xZr_xO₂ catalyst

Sample	S_BET/(m²·g⁻¹)	Pore volume/ (cm³·g⁻¹)	Average pore size/nm
CuO	8.2	0.027	12.9
Cu_0.99Zr_0.01O₂	14.3	0.044	11.2
Cu_0.95Zr_0.05O₂	18.3	0.067	12.1
Cu_0.75Zr_0.25O₂	55.3	0.152	9.0
Cu_0.60Zr_0.40O₂	59.5	0.128	7.5
Cu_0.40Zr_0.60O₂	106.6	0.194	5.8
ZrO₂	118.5	0.249	6.5

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表 3 不同Zr含量Cu_1−xZr_xO₂催化剂催化活性

Table 3 Evaluation of catalytic activity of the Cu_1−xZr_xO₂ catalyst

Sample	Conversion of glycerol/%	Selectivity of GC/%	Yield of GC/%
Blank	34.3	11.7	4.0
CuO	67.9	73.9	50.2
Cu_0.99Zr_0.01O₂	64.1	85.9	55.1
Cu_0.95Zr_0.05O₂	61.1	85.2	52.1
Cu_0.75Zr_0.25O₂	59.7	79.3	47.3
Cu_0.60Zr_0.40O₂	65.6	74.4	48.8
Cu_0.40Zr_0.60O₂	51.3	91.0	46.7
ZrO₂	34.0	11.8	4.0
Reaction conditions: glycerol 0.92 g, 2-cyanopyridine 3.26 g, DMF 10 mL, 120 ℃, 5 h, p(CO₂) = 3 MPa.

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参考文献(51)

[1]	HÖÖK M, TANGANG X. Depletion of fossil fuels and anthropogenic climate change—A review[J]. Energy policy,2013,52:797−809. doi: 10.1016/j.enpol.2012.10.046
[2]	WANG Y, NIU C, WANG D. Metallic nanocatalysts for electrochemical CO₂ reduction in aqueous solutions[J]. J Colloid Interface Sci,2018,527:95−106. doi: 10.1016/j.jcis.2018.05.041
[3]	HUANG C H, TAN C S. A review: CO₂ utilization[J]. Aerosol Air Qual Res,2014,14(2):480−499. doi: 10.4209/aaqr.2013.10.0326
[4]	KNUTSON T R, TULEYA R E. Impact of CO₂-induced warming on simulated hurricane intensity and precipitation: Sensitivity to the choice of climate model and convective parameterization[J]. J Clim,2004,17(18):3477−3495. doi: 10.1175/1520-0442(2004)017<3477:IOCWOS>2.0.CO;2
[5]	SONG L, JIANG Y X, ZHANG Z, et al. CO₂=CO+: Recent advances in carbonylation of C-H bonds with CO₂[J]. ChemComm,2020,56(60):8355−8367.
[6]	MATTIA D, JONES M D, O'BYRNE J P, et al. Towards carbon-neutral CO₂ conversion to hydrocarbons[J]. ChemSusChem,2015,8(23):4064−4072. doi: 10.1002/cssc.201500739
[7]	RAHPEYMA S S, RAHEB J. Microalgae biodiesel as a valuable alternative to fossil fuels[J]. Bioenergy Res,2019,12(4):958−965. doi: 10.1007/s12155-019-10033-6
[8]	SINGH D, SHARMA D, SONI S L, et al. A review on feedstocks, production processes, and yield for different generations of biodiesel[J]. Fuel,2020,262:116553. doi: 10.1016/j.fuel.2019.116553
[9]	MONTERIRO M R, KUGELMEIER C L, PINHEIRO R S, et al. Glycerol from biodiesel production: Technological paths for sustainability[J]. Renewable Sustainable Energy Rev,2018,88:109−122. doi: 10.1016/j.rser.2018.02.019
[10]	SUN D, YAMADA Y, SATO S, et al. Glycerol hydrogenolysis into useful C3 chemicals[J]. Appl Catal B: Environ,2016,193:75−92. doi: 10.1016/j.apcatb.2016.04.013
[11]	WU F, JIANG H, ZHU X, et al. Effect of tungsten species on selective hydrogenolysis of glycerol to 1, 3-propanediol[J]. ChemSusChem,2021,14(2):569−581. doi: 10.1002/cssc.202002405
[12]	TORRES S, PALACIO R, LÓPEZ D. Support effect in Co₃O₄-based catalysts for selective partial oxidation of glycerol to lactic acid[J]. Appl Catal A: Gen,2021,621:118199. doi: 10.1016/j.apcata.2021.118199
[13]	YAN H, SHEN Q, SUN Y, et al. Tailoring facets of α-Mn₂O₃ microcrystalline catalysts for enhanced selective oxidation of glycerol to glycolic acid[J]. ACS Catal,2021,11(11):6371−6383. doi: 10.1021/acscatal.1c01566
[14]	YAN H, YAO S, ZHAO S, et al. Insight into the basic strength-dependent catalytic performance in aqueous phase oxidation of glycerol to glyceric acid[J]. Chem Eng Sci,2021,230:116191. doi: 10.1016/j.ces.2020.116191
[15]	TAMOŠIĖŪNAS A, GIMŽAUSKAITĖ D, USCILA R, et al. Thermal arc plasma gasification of waste glycerol to syngas[J]. Appl Energy,2019,251:113306. doi: 10.1016/j.apenergy.2019.113306
[16]	HU J, LI J, GU Y, et al. Oxidative carbonylation of glycerol to glycerol carbonate catalyzed by PdCl₂ (phen)/KI[J]. Appl Catal A: Gen,2010,386(1/2):188−193. doi: 10.1016/j.apcata.2010.07.059
[17]	CHRISTY S, NOSCHESE A, LOMELI-RODRIGUEZ M, et al. Recent progress in the synthesis and applications of glycerol carbonate[J]. Curr Opin Green Sustainable Chem,2018,14:99−107. doi: 10.1016/j.cogsc.2018.09.003
[18]	ZHANG P, ZHU M, FAN M, et al. Rare earth-doped calcium-based magnetic catalysts for transesterification of glycerol to glycerol carbonate[J]. J Chin Chem Soc,2019,66(2):164−170. doi: 10.1002/jccs.201800164
[19]	LI Y, LIU J, HE D. Catalytic synthesis of glycerol carbonate from biomass-based glycerol and dimethyl carbonate over Li-La₂O₃ catalysts[J]. Appl Catal A: Gen,2018,564:234−242. doi: 10.1016/j.apcata.2018.07.032
[20]	SHUKLA K, SRIVASTAVA V C. Synthesis of organic carbonates from alcoholysis of urea: A review[J]. Catal Rev,2017,59(1):1−43. doi: 10.1080/01614940.2016.1263088
[21]	WU Y, SONG X, CAI F, et al. Synthesis of glycerol carbonate from glycerol and diethyl carbonate over Ce-NiO catalyst: The role of multiphase Ni[J]. J Alloys Compd,2017,720:360−368. doi: 10.1016/j.jallcom.2017.05.292
[22]	ARESTA M, DIBENEDETTO A, NOCITO F, et al. A study on the carboxylation of glycerol to glycerol carbonate with carbon dioxide: the role of the catalyst, solvent and reaction conditions[J]. J Mol Catal A: Chem,2006,257(1/2):149−153. doi: 10.1016/j.molcata.2006.05.021
[23]	PARK C, NGUYEN-PHU H, SHIN E W. Glycerol carbonation with CO₂ and La₂O₂CO₃/ZnO catalysts prepared by two different methods: Preferred reaction route depending on crystalline structure[J]. Mol Catal,2017,435:99−109. doi: 10.1016/j.mcat.2017.03.025
[24]	OCHOA-GÓMEZ J R, GÓMEZ-JIMÉNEZ-ABERASTURI O, RAMIREZ-LOPEZ C, et al. A brief review on industrial alternatives for the manufacturing of glycerol carbonate, a green chemical[J]. Org Process Res Dev,2012,16(3):389−399. doi: 10.1021/op200369v
[25]	SU X, LIN W, CHENG H, et al. Metal-free catalytic conversion of CO₂ and glycerol to glycerol carbonate[J]. Green Chem,2017,19(7):1775−1781. doi: 10.1039/C7GC00260B
[26]	LI J, WAMG T. Chemical equilibrium of glycerol carbonate synthesis from glycerol[J]. J Chem Thermodyn,2011,43(5):731−736. doi: 10.1016/j.jct.2010.12.013
[27]	VIEVILLE C, YOO J W, PELET S, et al. Synthesis of glycerol carbonate by direct carbonatation of glycerol in supercritical CO₂ in the presence of zeolites and ion exchange resins[J]. Catal Lett,1998,56(4):245−247. doi: 10.1023/A:1019050205502
[28]	DIBENEDETTO A, ANGELINI A, ARESTA M, et al. Converting wastes into added value products: from glycerol to glycerol carbonate, glycidol and epichlorohydrin using environmentally friendly synthetic routes[J]. Tetrahedron,2011,67(6):1308−1313. doi: 10.1016/j.tet.2010.11.070
[29]	GEORGE J, PATEL Y, PILLAI S M, et al. Methanol assisted selective formation of 1, 2-glycerol carbonate from glycerol and carbon dioxide using ⁿBu₂SnO as a catalyst[J]. J Mol Catal A: Chem,2009,304(1/2):1−7. doi: 10.1016/j.molcata.2009.01.010
[30]	LI H, JIAO X, LI L, et al. Synthesis of glycerol carbonate by direct carbonylation of glycerol with CO₂ over solid catalysts derived from Zn/Al/La and Zn/Al/La/M (M=Li, Mg and Zr) hydrotalcites[J]. Catal Sci Technol,2015,5(2):989−1005. doi: 10.1039/C4CY01237B
[31]	LIU Z, LI B, QIAO F, et al. Catalytic performance of Li/Mg composites for the synthesis of glycerol carbonate from glycerol and dimethyl carbonate[J]. ACS Omega,2022,7(6):5032−5038. doi: 10.1021/acsomega.1c05968
[32]	DOSUNA-RODRÍGUEZ I, GAIGNEAUX E M. Glycerol acetylation catalysed by ion exchange resins[J]. Catal Today,2012,195(1):14−21. doi: 10.1016/j.cattod.2012.04.031
[33]	LIU J, LI Y, ZHANG J, et al. Glycerol carbonylation with CO₂ to glycerol carbonate over CeO₂ catalyst and the influence of CeO₂ preparation methods and reaction parameters[J]. Appl Catal A: Gen,2016,513:9−18. doi: 10.1016/j.apcata.2015.12.030
[34]	MA J, SONG J, LIU H, et al. One-pot conversion of CO₂ and glycerol to value-added products using propylene oxide as the coupling agent[J]. Green Chem,2012,14(6):1743−1748. doi: 10.1039/c2gc35150a
[35]	AKHAVAN O, AZIMIRAD R, SAFA S, et al. CuO/Cu(OH)₂ hierarchical nanostructures as bactericidal photocatalysts[J]. J Mater Chem A,2011,21(26):9634−9640. doi: 10.1039/c0jm04364h
[36]	BENJARAM M R, ATAULLAH K. Recent advances on TiO₂-ZrO₂ mixed oxides as catalysts and catalyst supports[J]. Catal Rev,2005,47:257−296. doi: 10.1081/CR-200057488
[37]	LIU G, LIU J, LI W, et al. Aerobic oxidation of alcohols over Ru-Mn-Ce and Ru-Co-Ce catalysts: The effect of calcination temperature[J]. Appl Catal A: Gen,2017,535:77−84. doi: 10.1016/j.apcata.2017.02.006
[38]	GANDHE A R, REBELLO J S, FIGUEIREDO J L, et al. Manganese oxide OMS-2 as an effective catalyst for total oxidation of ethyl acetate[J]. Appl Catal B: Environ,2007,72(1/2):129−135. doi: 10.1016/j.apcatb.2006.10.017
[39]	KONDAWAR S E, POTDAR A S, RODE C V. Solvent-free carbonylation of glycerol with urea using metal loaded MCM-41 catalysts[J]. RSC Adv,2015,5(21):16452−16460. doi: 10.1039/C4RA11590B
[40]	ZHAO M, YAN H, LU R, et al. Insight into the selective oxidation mechanism of glycerol to 1, 3-dihydroxyacetone over AuCu-ZnO interface[J]. AIChE,2022,68(11):e17833. doi: 10.1002/aic.17833
[41]	LI D, WANG Z, HUANG J, et al. Ultrafine CeO₂ nanodots embedded in porous ZrO₂ for efficient and sustainable chlorine recycle through hydrochloric acid catalytic oxidation[J]. ChemistrySelect,2020,5(40):12442−12449. doi: 10.1002/slct.202003184
[42]	LIU B, LI C, ZHANG G, et al. Oxygen vacancy promoting dimethyl carbonate synthesis from CO₂ and methanol over Zr-doped CeO₂ nanorods[J]. ACS Catal,2018,8(11):10446−10456. doi: 10.1021/acscatal.8b00415
[43]	CLIMENT M J, CORMA A, DE FRUTOS P, et al. Chemicals from biomass: Synthesis of glycerol carbonate by transesterification and carbonylation with urea with hydrotalcite catalysts. The role of acid-base pairs[J]. J Catal,2010,269(1):140−149. doi: 10.1016/j.jcat.2009.11.001
[44]	LIU P, DERCHI M, HENSEN E J M. Promotional effect of transition metal doping on the basicity and activity of calcined hydrotalcite catalysts for glycerol carbonate synthesis[J]. Appl Catal B: Environ,2014,144:135−143. doi: 10.1016/j.apcatb.2013.07.010
[45]	ZHAO H, FANG K, ZHOU J, et al. Direct synthesis of methyl formate from syngas on Cu-Mn mixed oxide catalyst[J]. Int J Hydrog Energy,2016,41(21):8819−8828. doi: 10.1016/j.ijhydene.2016.03.149
[46]	GAO Z, ZHOU Z, WANG M, et al. Highly dispersed Pd anchored on heteropolyacid modified ZrO₂ for high efficient hydrodeoxygenation of lignin-derivatives[J]. Fuel,2023,334:126768. doi: 10.1016/j.fuel.2022.126768
[47]	MEGHA, MONDAL K, GHANTY T K, et al. Adsorption and activation of CO₂ on small-sized Cu-Zr bimetallic clusters[J]. J Phys Chem A,2021,125(12):2558−2572. doi: 10.1021/acs.jpca.1c00751
[48]	HONDA M, TAMURA M, NAKAO K, et al. Direct cyclic carbonate synthesis from CO₂ and diol over carboxylation/hydration cascade catalyst of CeO₂ with 2-cyanopyridine[J]. ACS Catal,2014,4(6):1893−1896. doi: 10.1021/cs500301d
[49]	MA J, LIU J, ZHANG Z, et al. Mechanisms of ethylene glycol carbonylation with carbon dioxide[J]. Comput Theor Chem,2012,992:103−109. doi: 10.1016/j.comptc.2012.05.010
[50]	DI COSIMO J I, DIEZ V K, XU M, et al. Structure and surface and catalytic properties of Mg-Al basic oxides[J]. J Catal,1998,178(2):499−510. doi: 10.1006/jcat.1998.2161
[51]	ZHANG J, HE D. Surface properties of Cu/La₂O₃ and its catalytic performance in the synthesis of glycerol carbonate and monoacetin from glycerol and carbon dioxide[J]. J Colloid Interface Sci,2014,419:31−38. doi: 10.1016/j.jcis.2013.12.049